WorldWideScience

Sample records for hydrocarbon oxidation reaction

  1. Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

    Science.gov (United States)

    Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

    2012-10-02

    Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

  2. Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

    Science.gov (United States)

    Jachimowski, C. J.; Wilson, C. H.

    1980-01-01

    The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

  3. A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

    DEFF Research Database (Denmark)

    1999-01-01

    A process for producing an alcohol from a gaseous hydrocarbon, e.g. a lower alkane such as methane, via oxidative reaction of the hydrocarbon in a concentrated sulfuric acid medium in the presence of a catalyst employs an added catalyst comprising a substance selected from iodine, iodine compounds...

  4. Laboratory Studies of Hydrocarbon Oxidation Mechanisms

    Science.gov (United States)

    Orlando, J. J.; Tyndall, G. S.; Wallington, T. J.; Burkholder, J. B.; Bertman, S. B.; Chen, W.

    2001-12-01

    The oxidation of hydrocarbon species (alkanes, alkenes, halogenated species, and oxygenates of both natural and anthropogenic origin) in the troposphere leads to the generation of numerous potentially harmful secondary pollutants, such as ozone, organic nitrates and acids, and aerosols. These oxidations proceed via the formation of alkoxy radicals, whose complex chemistry controls the ultimate product distributions obtained. Studies of hydrocarbon oxidation mechanisms are ongoing at NCAR and Ford, using environmental chamber / FTIR absorption systems. The focus of these studies is often on the product distributions obtained at low temperature; these studies not only provide data of direct relevance to the free/upper troposphere, but also allow for a more fundamental understanding of the alkoxy radical chemistry (eg., from the determination of the Arrhenius parameters for unimolecular processes, and the quantification of the extent of the involvement of chemical activation in the alkoxy radical chemistry). In this paper, data will be presented on some or all of the following topics: kinetics/mechanisms for the reactions of OH with the unsaturated species MPAN, acrolein, and crotonaldehyde; the mechanism for the oxidation of ethyl chloride and ethyl bromide; and the mechanism for the reaction of OH with acetone and acetaldehyde at low temperature. The relevance of the data to various aspects of tropospheric chemistry will be discussed.

  5. Isotopes in oxidation reactions

    International Nuclear Information System (INIS)

    Stewart, R.

    1976-01-01

    The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

  6. Nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Osipova, Z.G.; Sokolovskii, V.D.

    1979-03-01

    The nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst GaSbNiPOx (1:3:1.5:1 atomic ratios of the elements) was studied by comparing the rate of this reaction at 550/sup 0/C and 5Vertical Bar3< by vol propane/6Vertical Bar3< ammonia/18.6Vertical Bar3< oxygen/70.4Vertical Bar3< helium reactant mixture with that of isobutane ammoxidation to methacrylonitrile under the same conditions, at low (Vertical Bar3; 20Vertical Bar3<) conversions that prevent secondary oxidation of the products. Both the over-all hydrocarbon conversion rate and that of nitrile formation were higher for propane, suggesting that the reactions proceed via the respective carbanions (probably primary carbanions), rather than carbocations or uncharged radicals.

  7. Interaction of oxides of nitrogen and aromatic hydrocarbons under simulated atmospheric conditions

    International Nuclear Information System (INIS)

    Obrien, R.J.; Green, P.J.; Doty, R.A.; Vanderzanden, J.W.; Easton, R.R.; Irwin, R.P.

    1979-01-01

    The reactions of nitrogen oxides with aromatic hydrocarbons under simulated atmospheric conditions are investigated. Gaseous reaction products formed when toluene is irradiated under simulated atmospheric conditions in the presence of nitrogen oxides were analyzed by gas chromatography. Reaction products detected include acetylene, water, acetaldehyde, acetone, toluene, benzaldehyde, ortho-, meta- and para-cresol, benzyl nitrate and meta- and para-nitrotoluene. Reaction mechanisms yielding the various products are illustrated. The assumption that all the nitrogen oxides observed to be lost from the reaction products can be accounted for by nitric acid formation in the absence of ozone formation is verified by a model in which the hydroxyl radical is assumed to be the only means of removing toluene. Under conditions in which ozone is formed, nitrogen oxide loss is accounted for by ozone formation in addition to nitric acid formation

  8. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...

  9. Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate

    Energy Technology Data Exchange (ETDEWEB)

    Forsey, S.P.; Thomson, N.R.; Barker, J.F. [University of Waterloo, Waterloo, ON (Canada). Dept. of Civil & Environmental Engineering

    2010-04-15

    The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalene < phenanthrene < pyrene. The rate of side chain reactivity is controlled by the C-H bond strength. For the alkyl substituted benzenes an excellent correlation was observed between the reaction rate coefficients and bond dissociation energies, but for the substituted PAHs the relationship was poor. A trend was found between the reaction rate coefficients and the calculated heats of complexation indicating that significant ring oxidation occurred in addition to side chain oxidation. Clar's aromatic sextet theory was used to predict the relative stability of arenes towards ring oxidation by permanganate.

  10. Formation of polycyclic aromatic hydrocarbons and soot in fuel-rich oxidation of methane in a laminar flow reactor

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Østberg, M.

    2004-01-01

    Conversion of methane to higher hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and soot was investigated under fuel-rich conditions in a laminar flow reactor. The effects of stoichiometry, dilution, and water vapor addition were studied at temperatures between 1073 and 1823 K. A chemical...... kinetic mechanism was established for methane oxidation, with emphasis on formation of higher hydrocarbons and PAH. A submodel for soot formation was adopted from the work of Frenklach and co-workers without changes. Modeling predictions showed good agreement with experimental results. Reactants, stable...... decrease with increasing addition of water vapor. The effect is described qualitatively by the reaction mechanism. The enhanced oxidation of acetylene is attributed to higher levels of hydroxyl radicals, formed from the reaction between the water vapor and hydrogen atoms....

  11. Mechanistic studies on the OH-initiated atmospheric oxidation of selected aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nehr, Sascha

    2012-07-01

    Benzene, toluene, the xylenes, and the trimethylbenzenes are among the most abundant aromatic trace constituents of the atmosphere mainly originating from anthropogenic sources. The OH-initiated atmospheric photo-oxidation of aromatic hydrocarbons is the predominant removal process resulting in the formation of O{sub 3} and secondary organic aerosol. Therefore, aromatics are important trace constituents regarding air pollution in urban environments. Our understanding of aromatic photo-oxidation processes is far from being complete. This work presents novel approaches for the investigation of OH-initiated atmospheric degradation mechanisms of aromatic hydrocarbons. Firstly, pulsed kinetic studies were performed to investigate the prompt HO{sub 2} formation from OH+ aromatic hydrocarbon reactions under ambient conditions. For these studies, the existing OH reactivity instrument, based on the flash photolysis/laser-induced fluorescence (FP/LIF) technique, was extended to the detection of HO{sub 2} radicals. The experimental design allows for the determination of HO{sub 2} formation yields and kinetics. Results of the pulsed kinetic experiments complement previous product studies and help to reduce uncertainties regarding the primary oxidation steps. Secondly, experiments with aromatic hydrocarbons were performed under atmospheric conditions in the outdoor atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber) located at Forschungszentrum Juelich. The experiments were aimed at the evaluation of up-to-date aromatic degradation schemes of the Master Chemical Mechanism (MCMv3.2). The unique combination of analytical instruments operated at SAPHIR allows for a detailed investigation of HO{sub x} and NO{sub x} budgets and for the determination of primary phenolic oxidation product yields. MCMv3.2 deficiencies were identified and most likely originate from shortcomings in the mechanistic representation of ring

  12. Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

    Science.gov (United States)

    Forsey, Steven P; Thomson, Neil R; Barker, James F

    2010-04-01

    The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalenepermanganate. 2010 Elsevier Ltd. All rights reserved.

  13. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    Science.gov (United States)

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  14. Reactions between 52100 steel and tricresyl phosphate neat and mixed with hydrocarbon oil

    International Nuclear Information System (INIS)

    Arezzo, F.; Moore, R.L.

    1987-01-01

    Some of the results from a previous study which showed reactions between iron surfaces (52100 steel) and tricresyl phosphate (TCP) dissolved in hydrocarbon oil are discussed in this paper. This study had shown that microscale oxidation of the hydrocarbon oil and preferential adsorption phenomena within the oil system components may result in a desirable phosphate type of coating. This phosphate is organic and it is converted into iron phosphate on argon ion sputtering. Also discussed in this paper are the results of a more recent work which shows the reactivity of neat TCP with an identical 52100 steel surface. The results of electron spectroscopy for chemical analysis indicate that neat TCP behaves quite differently from TCP diluted in hydrocarbon oil. The phosphate generated on the metal surface by neat TCP yields predominantly a phosphide when subjected to argon ion sputtering. (orig.)

  15. Effect of hydrocarbons on plasma treatment of NOx

    Energy Technology Data Exchange (ETDEWEB)

    Penetrante, B.M.; Pitz, W.J.; Hsaio, M.C.; Merritt, B.T.; Vogtlin, G.E. [Lawrence Livermore National Lab., CA (United States)

    1997-12-31

    Lean burn gasoline engine exhausts contain a significant amount of hydrocarbons in the form of propene. Diesel engine exhausts contain little gaseous hydrocarbon; however, they contain a significant amount of liquid-phase hydrocarbons (known as the volatile organic fraction) in the particulates. The objective of this paper is to examine the fate of NO{sub x} when an exhaust gas mixture that contains hydrocarbons is subjected to a plasma. The authors will show that the hydrocarbons promote the oxidation of NO to NO{sub 2}, but not the reduction of NO to N{sub 2}. The oxidation of NO to NO{sub 2} is strongly coupled with the hydrocarbon oxidation chemistry. This result suggests that gas-phase reactions in the plasma alone cannot lead to the chemical reduction of NO{sub x}. Any reduction of NO{sub x} to N{sub 2} can only be accomplished through heterogeneous reactions of NO{sub 2} with surfaces or particulates.

  16. Treatment of petroleum-hydrocarbon contaminated soils using hydrogen peroxide oxidation catalyzed by waste basic oxygen furnace slag

    International Nuclear Information System (INIS)

    Tsai, T.T.; Kao, C.M.

    2009-01-01

    The contamination of subsurface soils with petroleum hydrocarbons is a widespread environmental problem. The objective of this study was to evaluate the potential of applying waste basic oxygen furnace slag (BOF slag) as the catalyst to enhance the Fenton-like oxidation to remediate fuel oil or diesel contaminated soils. The studied controlling factors that affect the removal efficiency of petroleum hydrocarbons included concentrations of H 2 O 2 , BOF slag dosages, types of petroleum hydrocarbons (e.g., fuel oil and diesel), and types of iron mineral. Experimental results indicate that oxidation of petroleum hydrocarbon via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/sandy loam system was iron mineral (e.g., α-Fe 2 O 3 and α-FeOOH). Approximately 76% and 96% of fuel oil and diesel removal were observed (initial total petroleum hydrocarbon (TPH) concentration = 10,000 mg kg -1 ), respectively, with the addition of 15% of H 2 O 2 and 100 g kg -1 of BOF slag after 40 h of reaction. Because BOF slag contains extractable irons such as amorphous iron and soluble iron, it can act as an iron sink to supply iron continuously for Fenton-like oxidation. Results demonstrate that Fenton-like oxidation catalyzed by BOF slag is a potential method to be able to remediate petroleum-hydrocarbon contaminated soils efficiently and effectively.

  17. Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

    Science.gov (United States)

    Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

    2000-01-01

    In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

  18. Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Froehaug, Astrid Elisabeth

    1995-12-31

    This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

  19. Treatment of petroleum-hydrocarbon contaminated soils using hydrogen peroxide oxidation catalyzed by waste basic oxygen furnace slag

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, T.T. [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Kao, C.M., E-mail: jkao@mail.nsysu.edu.tw [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China)

    2009-10-15

    The contamination of subsurface soils with petroleum hydrocarbons is a widespread environmental problem. The objective of this study was to evaluate the potential of applying waste basic oxygen furnace slag (BOF slag) as the catalyst to enhance the Fenton-like oxidation to remediate fuel oil or diesel contaminated soils. The studied controlling factors that affect the removal efficiency of petroleum hydrocarbons included concentrations of H{sub 2}O{sub 2}, BOF slag dosages, types of petroleum hydrocarbons (e.g., fuel oil and diesel), and types of iron mineral. Experimental results indicate that oxidation of petroleum hydrocarbon via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/sandy loam system was iron mineral (e.g., {alpha}-Fe{sub 2}O{sub 3} and {alpha}-FeOOH). Approximately 76% and 96% of fuel oil and diesel removal were observed (initial total petroleum hydrocarbon (TPH) concentration = 10,000 mg kg{sup -1}), respectively, with the addition of 15% of H{sub 2}O{sub 2} and 100 g kg{sup -1} of BOF slag after 40 h of reaction. Because BOF slag contains extractable irons such as amorphous iron and soluble iron, it can act as an iron sink to supply iron continuously for Fenton-like oxidation. Results demonstrate that Fenton-like oxidation catalyzed by BOF slag is a potential method to be able to remediate petroleum-hydrocarbon contaminated soils efficiently and effectively.

  20. Photodegradation of polycyclic aromatic hydrocarbon pyrene by iron oxide in solid phase

    International Nuclear Information System (INIS)

    Wang, Y.; Liu, C.S.; Li, F.B.; Liu, C.P.; Liang, J.B.

    2009-01-01

    To better understand the photodegradation of polycyclic aromatic hydrocarbons (PAH) in solid phase in natural environment, laboratory experiments were conducted to study the influencing factors, kinetics and intermediate compound of pyrene photodegradation by iron oxides. The results showed that the pyrene photodegradation rate followed the order of α-FeOOH > α-Fe 2 O 3 > γ-Fe 2 O 3 > γ-FeOOH at the same reaction conditions. Lower dosage of α-FeOOH and higher light intensity increased the photodegradation rate of pyrene. Iron oxides and oxalic acid can set up a photo-Fenton-like system without additional H 2 O 2 in solid phase to enhance the photodegradation of pyrene under UV irradiation. All reaction followed the first-order reaction kinetics. The half-life (t 1/2 ) of pyrene in the system showed the higher efficiencies of using iron oxide as photocatalyst to degrade pyrene. Intermediate compound pyreno was found during photodegradation reactions by gas chromatography-mass spectrometry (GC-MS). The photodegradation efficiency for PAHs in this photo-Fenton-like system was also confirmed by using the contaminated soil samples. This work provides some useful information to understand the remediation of PAHs contaminated soils by photochemical techniques under practical condition

  1. The multichannel n-propyl + O2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism

    Science.gov (United States)

    Bartlett, Marcus A.; Liang, Tao; Pu, Liang; Schaefer, Henry F.; Allen, Wesley D.

    2018-03-01

    of hydrocarbon oxidation.

  2. Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

    Energy Technology Data Exchange (ETDEWEB)

    Que, Jr., Lawrence [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-03-22

    Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

  3. Reaction kinetics and reaction heat on thermal decomposition of solvent containing unstable reactive hydrocarbons with nitric acid at Tomsk-7 reprocessing plant

    International Nuclear Information System (INIS)

    Nishio, Gunji; Watanabe, Kouji; Koike, Tadao; Miyato, Teijiro.

    1996-12-01

    For analyzing a cause of the Tomsk-7 accident at Russian reprocessing plant, it is necessary to determine reaction-rate constant and reaction heat for a thermal decomposition of TBP/kerosine containing unstable reactive hydrocarbons with nitric acid. In JAERI, the rate constant and reaction heat were obtained from data measured with a differential thermal analyzer (DTA) for unstable hydrocarbons such as n-butanol, n-butyl nitrate, aromatic hydrocarbons, and cyclic compounds. The safety evaluation of Tomsk tank ruptured by the reaction was carried out by heat balance calculations between heat generation and heat loss in the tank using these rate constants and reaction heats. Consequently, it is clear that the cause of the tank rupture would be due to an exothermic reaction of aromatic hydrocarbons in kerosine made by petroleum with the concentrated nitric acid of 14.2N. (author)

  4. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet

    2012-11-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  5. Reaction mechanism for the free-edge oxidation of soot by O 2

    KAUST Repository

    Raj, Abhijeet; da Silva, Gabriel; Chung, Suk-Ho

    2012-01-01

    The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

  6. Electrochemical removal of NOx and hydrocarbons

    DEFF Research Database (Denmark)

    Friedberg, Anja Zarah

    on the electrodes during polarisation, probably because of strong adsorption of the hydrocarbon relative to NO. On LSF/CGO electrode the impregnation of ionic conducting material increased the oxidation of NO to NO2 which is an important step before nitrogen formation. The propene inhibited this reaction because....... This could only be done if the electrode was impregnated with BaO. The nitrate formation did not seem to be inhibited by the presence of the hydrocarbon. However, the oxidation of propene was inhibited by the BaO because the active sites for oxidations were partially covered by the BaO nanoparticles...

  7. Conversion of hydrocarbons in solid oxide fuel cells

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Kammer Hansen, K.

    2003-01-01

    Recently, a number of papers about direct oxidation of methane and hydrocarbon in solid oxide fuel cells (SOFC) at relatively low temperatures (about 700degreesC) have been published. Even though the conversion of almost dry CH4 at 1000degreesC on ceramic anodes was demonstrated more than 10 years...

  8. 40 CFR 89.112 - Oxides of nitrogen, carbon monoxide, hydrocarbon, and particulate matter exhaust emission standards.

    Science.gov (United States)

    2010-07-01

    ....112 Oxides of nitrogen, carbon monoxide, hydrocarbon, and particulate matter exhaust emission... emissions of oxides of nitrogen, carbon monoxide, hydrocarbon, and nonmethane hydrocarbon are measured using... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Oxides of nitrogen, carbon monoxide...

  9. Process for scavenging hydrogen sulfide from hydrocarbon gases

    International Nuclear Information System (INIS)

    Fox, I.

    1981-01-01

    A process for scavenging hydrogen sulfide from hydrocarbon gases utilizes iron oxide particles of unique chemical and physical properties. These particles have large surface area, and are comprised substantially of amorphous Fe 2 O 3 containing a crystalline phase of Fe 2 O 3 , Fe 3 O 4 and combinations thereof. In scavenging hydrogen sulfide, the iron oxide particles are suspended in a liquid which enters into intimate mixing contact with hydrocarbon gases; the hydrogen sulfide is reacted at an exceptional rate and only acid-stable reaction products are formed. Thereafter, the sweetened hydrocarbon gases are collected

  10. Ionic Conductivity and its Role in Oxidation Reactions

    Science.gov (United States)

    Tamimi, Mazin Abdulla

    In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

  11. Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Wesley D. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry; Schaefer, III, Henry F. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry

    2015-11-14

    This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.

  12. Cobalt/N-Hydroxyphthalimide(NHPI)-Catalyzed Aerobic Oxidation of Hydrocarbons with Ionic Liquid Additive

    DEFF Research Database (Denmark)

    Mahmood, Sajid; Xu, Bao Hua; Ren, Tian Lu

    2018-01-01

    A highly efficient and solvent-free system of cobalt/NHPI-catalyzed aerobic oxidation of hydrocarbons was developed using imidazolium-based ionic liquid (IL) as an additive. These amphipathic ILs were found self-assemble at the interface between the organic hydrocarbons and the aqueous phase...... the optimum reactivity. Besides, the interfacial boundary between aqueous and organic phase composed by C2-alkylated imidazolium ILs, such as [bdmim]SbF6 and [C12dmim]SbF6, not only has ternary aggregates (hydrocarbons/IL/H2O) of higher stability but renders O2 a faster diffusion rate and higher concentration......, thereby offering a high reactivity of the protocol towards hydrocarbon oxidation....

  13. Wet Oxidation of Fine Soil Contaminated with Petroleum Hydrocarbons: A Way towards a Remediation Cycle

    Directory of Open Access Journals (Sweden)

    Maria Cristina Collivignarelli

    2018-06-01

    Full Text Available The aim of this experimental study was to assess the feasibility of using a wet oxidation (WO process for treating fine soil with a high level of total petroleum hydrocarbons (TPHs. Two samples of soil were spiked with two different contaminants (motor oil, and motor oil + diesel. The samples were subjected to a WO bench plant test, where the effect of the main process parameters (i.e., temperature and reaction time on the removal of TPHs was investigated. Results show that the WO process is effective for the decontamination of hydrocarbons, and a strong reduction (>85% can be obtained with the typical working conditions of a full-scale plant (temperature = 250 °C, reaction time = 30 min. The solid residue resulting from the WO process was characterized in order to evaluate the recovery options. In terms of chemical characterization, the contents of the pollutants comply with the Italian regulations for commercial and industrial site use. Moreover, the results of the leaching test suggested that these residues could be reused for ceramic and brick manufacturing processes.

  14. On energetics of hydrocarbon chemical reactions by ionizing irradiation

    International Nuclear Information System (INIS)

    Zaykin, Yu.A.; Zaykina, R.F.; Mirkin, G.

    2002-01-01

    Complete text of publication follows. The present global energy crisis requires the industry to look for technologies that are more effective and, particularly, less energy consuming. The hydrocarbon processing technology based on the electron radiation-induced thermal chemical conversion has a great potential. Comparing the presently predominant thermocatalytic processing, it is much more energy efficient, because chemical conversions go at a minimal processing temperature and pressure. To compare energy consumption by electron irradiation with thermal and thermocatalytic technologies of hydrocarbon processing one must see major differences between them. While traditional thermocatalytic processes are equilibrium and their energetics can be evaluated based on principles of classic thermodynamics, HEET processing is non-equilibrium and this evaluation approach is not valid for it. However, a theoretical description of radiation-chemical conversion using reaction rate constants determined in thermally equilibrium systems is approximately adequate to radiation processes by substituting equilibrium concentrations of reacting particles as their non-equilibrium concentrations under irradiation. In particular, description of radical reactions initiated by radiation requires substitution of thermally equilibrium radical concentration by much higher concentration defined by the dynamic equilibrium of radical radiation generation and their recombination. The paper presents the comparative analysis of energy consumption in different stages of hydrocarbon processing using classic thermal cracking by heating versus radiation induced cracking. It is shown that in the most energy-consuming stage of processing - the chain reaction initiation necessary for concentration of active radicals, irradiation processing has the great advantage compared to thermal cracking by heating and allows cutting down the total energy consumption by approximately 40%

  15. Effects of non-thermal plasmas and electric field on hydrocarbon/air flames

    Science.gov (United States)

    Ganguly, Biswa

    2009-10-01

    Need to improve fuel efficiency, and reduce emission from hydrocarbon combustor in automotive and gas turbine engines have reinvigorated interest in reducing combustion instability of a lean flame. The heat generation rate in a binary reaction is HQ =N^2 c1c2 Q exp(-E/RT), where N is the density, c1 and c2 are mol fractions of the reactants, Q is the reaction heat release, E is the activation energy, R is the gas constant and T is the average temperature. For hydrocarbon-air reactions, the typical value of E/R ˜20, so most heat release reactions are confined to a thin reaction sheet at T >=1400 K. The lean flame burning condition is susceptible to combustion instability due to a critical balance between heat generation and heat loss rates, especially at high gas flow rate. Radical injection can increase flame speed by reducing the hydrocarbon oxidation reaction activation barrier and it can improve flame stability. Advances in nonequilibrium plasma generation at high pressure have prompted its application for energy efficient radical production to enhance hydrocarbon-air combustion. Dielectric barrier discharges and short pulse excited corona discharges have been used to enhance combustion stability. Direct electron impact dissociation of hydrocarbon and O2 produces radicals with lower fuel oxidation reaction activation barriers, initiating heat release reaction CnHm+O CnHm-1+ OH (and other similar sets of reactions with partially dissociated fuel) below the typical cross-over temperature. Also, N2 (A) produced in air discharge at a moderate E/n can dissociate O2 leading to oxidation of fuel at lower gas temperature. Low activation energy reactions are also possible by dissociation of hydrocarbon CnHm+e -> CnHm-2+H2+e, where a chain propagation reaction H2+ O OH+H can be initiated at lower gas temperature than possible under thermal equilibrium kinetics. Most of heat release comes from the reaction CO+OH-> CO2 +H, nonthermal OH production seem to improve

  16. Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

    Science.gov (United States)

    Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

    2008-02-13

    Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

  17. A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

    KAUST Repository

    Raj, Abhijeet

    2012-02-01

    This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline surrogate fuels with the largest chemical species being pyrene (C 16H 10), this new mechanism is generated by adding PAH sub-mechanisms to account for the formation and growth of PAHs up to coronene (C 24H 12). The density functional theory (DFT) and the transition state theory (TST) have been adopted to evaluate the rate constants for several PAH reactions. The mechanism is validated in the premixed laminar flames of n-heptane, iso-octane, benzene and ethylene. The characteristics of PAH formation in the counterflow diffusion flames of iso-octane/toluene and n-heptane/toluene mixtures have also been tested for both the soot formation and soot formation/oxidation flame conditions. The predictions of the concentrations of large PAHs in the premixed flames having available experimental data are significantly improved with the new mechanism as compared to the base mechanism. The major pathways for the formation of large PAHs are identified. The test of the counterflow diffusion flames successfully predicts the PAH behavior exhibiting a synergistic effect observed experimentally for the mixture fuels, irrespective of the type of flame (soot formation flame or soot formation/oxidation flame). The reactions that lead to this synergistic effect in PAH formation are identified through the rate-of-production analysis. © 2011 The Combustion Institute.

  18. Problems of selectivity in liquid-phase oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Emanuel, N M

    1978-07-01

    Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

  19. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  20. The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

    International Nuclear Information System (INIS)

    Goodman, D.W.; Haw, J.F.; Lunsford, J.

    1998-01-01

    'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

  1. Atmospheric oxidation of selected hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Olariu, R.I.

    2002-02-01

    This work presents investigations on the gas-phase chemistry of phenol and the cresol isomers performed in a 1080 l quartz glass reactor in Wuppertal and in a large-volume outdoor photoreactor EUPHORE in Valencia, Spain. The studies aimed at clarifying the oxidation mechanisms of the reactions of these compounds with OH and NO{sub 3} radicals. Product investigations on the oxidation of phenol and the cresol isomers initiated by OH radicals were performed in the 1080 l quartz glass reactor with analyses by in situ FT-IR absorption spectroscopy. The primary focus of the investigations was on the determination of product yields. This work represents the first determination and quantification of 1,2-dihydroxybenzenes in the OH oxidation of phenolic compounds. Possible reaction pathways leading to the observed products have been elucidated. (orig.)

  2. Anaerobic Microbial Degradation of Hydrocarbons: From Enzymatic Reactions to the Environment.

    Science.gov (United States)

    Rabus, Ralf; Boll, Matthias; Heider, Johann; Meckenstock, Rainer U; Buckel, Wolfgang; Einsle, Oliver; Ermler, Ulrich; Golding, Bernard T; Gunsalus, Robert P; Kroneck, Peter M H; Krüger, Martin; Lueders, Tillmann; Martins, Berta M; Musat, Florin; Richnow, Hans H; Schink, Bernhard; Seifert, Jana; Szaleniec, Maciej; Treude, Tina; Ullmann, G Matthias; Vogt, Carsten; von Bergen, Martin; Wilkes, Heinz

    2016-01-01

    Hydrocarbons are abundant in anoxic environments and pose biochemical challenges to their anaerobic degradation by microorganisms. Within the framework of the Priority Program 1319, investigations funded by the Deutsche Forschungsgemeinschaft on the anaerobic microbial degradation of hydrocarbons ranged from isolation and enrichment of hitherto unknown hydrocarbon-degrading anaerobic microorganisms, discovery of novel reactions, detailed studies of enzyme mechanisms and structures to process-oriented in situ studies. Selected highlights from this program are collected in this synopsis, with more detailed information provided by theme-focused reviews of the special topic issue on 'Anaerobic biodegradation of hydrocarbons' [this issue, pp. 1-244]. The interdisciplinary character of the program, involving microbiologists, biochemists, organic chemists and environmental scientists, is best exemplified by the studies on alkyl-/arylalkylsuccinate synthases. Here, research topics ranged from in-depth mechanistic studies of archetypical toluene-activating benzylsuccinate synthase, substrate-specific phylogenetic clustering of alkyl-/arylalkylsuccinate synthases (toluene plus xylenes, p-cymene, p-cresol, 2-methylnaphthalene, n-alkanes), stereochemical and co-metabolic insights into n-alkane-activating (methylalkyl)succinate synthases to the discovery of bacterial groups previously unknown to possess alkyl-/arylalkylsuccinate synthases by means of functional gene markers and in situ field studies enabled by state-of-the-art stable isotope probing and fractionation approaches. Other topics are Mo-cofactor-dependent dehydrogenases performing O2-independent hydroxylation of hydrocarbons and alkyl side chains (ethylbenzene, p-cymene, cholesterol, n-hexadecane), degradation of p-alkylated benzoates and toluenes, glycyl radical-bearing 4-hydroxyphenylacetate decarboxylase, novel types of carboxylation reactions (for acetophenone, acetone, and potentially also benzene and

  3. Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

    1996-11-01

    Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

  4. Electrode Design for Low Temperature Direct-Hydrocarbon Solid Oxide Fuel Cells

    Science.gov (United States)

    Chen, Fanglin (Inventor); Zhao, Fei (Inventor); Liu, Qiang (Inventor)

    2015-01-01

    In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

  5. Electrode design for low temperature direct-hydrocarbon solid oxide fuel cells

    Science.gov (United States)

    Chen, Fanglin; Zhao, Fei; Liu, Qiang

    2015-10-06

    In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

  6. Hydrogen or Soot?: Partial Oxidation of High-boiling Hydrocarbon Wastes

    Czech Academy of Sciences Publication Activity Database

    Lederer, J.; Hanika, Jiří; Nečesaný, F.; Poslední, W.; Tukač, V.; Veselý, Václav

    2015-01-01

    Roč. 29, č. 1 (2015), s. 5-11 ISSN 0352-9568 Institutional support: RVO:67985858 Keywords : partial oxidation * waste * hydrocarbon Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.675, year: 2015

  7. Enhancement of in situ Remediation of Hydrocarbon Contaminated Soil

    Energy Technology Data Exchange (ETDEWEB)

    Palmroth, M.

    2006-07-01

    Approximately 750 000 sites of contaminated land exist across Europe. The harmful chemicals found in Finnish soils include heavy metals, oil products, polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorophenols, and pesticides. Petroleum and petroleum products enter soil from ruptured oil pipelines, land disposal of refinery products, leaking storage tanks and through accidents. PAH contamination is caused by the spills of coal tar and creosote from coal gasification and wood treatment sites in addition to oil spills. Cleanup of soil by bioremediation is cheaper than by chemical and physical processes. However, the cleaning capacity of natural attenuation and in situ bioremediation is limited. The purpose of this thesis was to find feasible options to enhance in situ remediation of hydrocarbon contaminants. The aims were to increase the bioavailability of the contaminants and microbial activity at the subsurface in order to achieve higher contaminant removal efficiency than by intrinsic biodegradation alone. Enhancement of microbial activity and decrease of soil toxicity during remediation were estimated by using several biological assays. The performance of these assays was compared in order to find suitable indicators to follow the progress of remediation. Phytoremediation and chemical oxidation are promising in situ techniques to increase the degradation of hydrocarbons in soil. Phytoremediation is plant-enhanced decontamination of soil and water. Degradation of hydrocarbons is enhanced in the root zone by increased microbial activity and through the detoxifying enzymes of plants themselves. Chemical oxidation of contaminants by Fenton's reaction can produce degradation products which are more biodegradable than the parent compounds. Fenton's reaction and its modifications apply solutions of hydrogen peroxide and iron for the oxidation of organic chemicals. The cost of oxidation can be reduced by aiming at partial instead of full

  8. Effect of temperature on photochemical smog reactions

    Energy Technology Data Exchange (ETDEWEB)

    Bufalini, J J; Altshuller, A P

    1963-01-01

    In the present investigation the photo-oxidation reactions to trans-2-butene-nitric oxide and 1,3,5-trimethylbenzene (mesitylene)-nitric oxide in air have been followed. The rates of formation and disappearance of nitrogen dioxide and the rate of reaction of the hydrocarbons have been measured at 20 and 40/sup 0/. The results obtained indicate about a twofold decrease in conversion times over the 20/sup 0/ interval and a corresponding increase in rates of reactions. 5 references.

  9. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  10. Upgrading of syngas hydrotreated fractionated oxidized bio-oil to transportation grade hydrocarbons

    International Nuclear Information System (INIS)

    Luo, Yan; Hassan, El Barbary; Guda, Vamshi; Wijayapala, Rangana; Steele, Philip H.

    2016-01-01

    Highlights: • Hydrotreating of fractionated oxidized bio-oil with syngas was feasible. • Hydrocarbon properties were similar with all syngas H_2/CO molar ratios except viscosity. • Syngas with H_2/CO molar ratio of (4:6) produced the highest hydrocarbon yield. • The produced hydrocarbons were in the range of gasoline, jet fuel and diesel boiling points. - Abstract: Fast pyrolysis bio-oils have the potential to replace a part of transportation fuels obtained from fossil. Bio-oil can be successfully upgraded into stable hydrocarbons (gasoline, jet fuel and diesel) through a two-stage hydrodeoxygenation process. Consumption large amount of expensive hydrogen during this process is the major hurdle for commercialization of this technology. Applying syngas in the hydrotreating step can significantly reduce the cost of the whole process and make it competitive. In this study, four different models of syngas with different H_2 concentrations (H_2/CO molar ratios = 2:8, 4:6, 6:4 and 8:2) were used for the 1st-stage hydrotreating step of oxidized fractionated bio-oil (OFB). The 2nd-stage hydrocracking step was performed on the produced organic liquid products (OLPs) by using pure H_2 gas. The effect of syngas H_2 concentrations on the yields and properties of OLPs and the 2nd-stage hydrocarbons (HCs) was investigated. Physical and chemical properties of the 2nd-stage hydrocarbons were similar regardless syngas H_2 content, with the exception of the viscosity. Syngas with H_2/CO molar ratio of 4:6 gave significantly highest HCs yield (24.8 wt.%) based on the OFB. Simulated distillation analysis proved that all 2nd-stage hydrocarbons were mixture from a wide range boiling point fuels. These results also indicated that the successful 1st-stage syngas hydrotreating step was having the potential to produce different hydrocarbons.

  11. Cordierite-supported metal oxide for non-methane hydrocarbon oxidation in cooking oil fumes.

    Science.gov (United States)

    Huang, Yonghai; Yi, Honghong; Tang, Xiaolong; Zhao, Shunzheng; Gao, Fengyu; Wang, Jiangen; Yang, Zhongyu

    2018-05-21

    Cooking emission is an important reason for the air quality deterioration in the metropolitan area in China. Transition metal oxide and different loading of manganese oxide supported on cordierite were prepared by incipient wetness impregnation method and were used for non-methane hydrocarbon (NMHC) oxidation in cooking oil fumes (COFs). The effects of different calcination temperature and different Mn content were also studied. The SEM photographs and CO 2 temperature-programmed desorption revealed 5 wt% Mn/cordierite had the best pore structure and the largest number of the weak and moderate basic sites so it showed the best performance for NMHC oxidation. XRD analysis exhibited 5 wt% Mn/cordierite had the best dispersion of active phase and the active phase was MnO 2 when the calcination temperature was 400℃ which were good for the catalytic oxidation of NMHC.

  12. Analysis of Oxidative Stress in Chronic Exposure to Petroleum Hydrocarbons in Karnataka, India

    Directory of Open Access Journals (Sweden)

    Suttur Malini

    2017-03-01

    Full Text Available Background:Several studies have reported the toxicological implications of inhalation of petroleum hydrocarbon fumes in animal models. But, there is certainly little or no documentation of the exposure to petroleum hydrocarbon fuel on oxidative stress levels in humans, unlike the pulmonary physiology. The present study was carried out to evaluate the effects of constituents of the hydrocarbon fuels on oxidative stress levels of the petrol fillers and tanker drivers. Methods: The study involved 165 males divided into three groups were the petrol fillers, tanker drivers and the controls. Case control data set was established wherein the control subjects are not exposed to hydrocarbon fuels with similar age. Serum samples of the subjects were collected and subjected for various biochemical assays. The enzymatic antioxidants such as superoxide dismutase, malondialdehyde a byproduct of lipid peroxidation and total antioxidant capacity of the individuals along with non-enzymatic antioxidant Vitamin A was estimated. Results: The results showed a no significant differences for age, body mass index, superoxide dismutase and levels of Malondialdehyde and total antioxidant capacity. But on the other hand, there is significant changes observed for total antioxidant capacity and vitamin A when exposed group is compared with control subject. Conclusion: It is evidential from the present study that prolonged exposure to petroleum hydrocarbon fumes leads to an increase in their oxidative stress in turn resulting broad spectrum of diseases. Hence, there is a raised need for public awareness about the health hazards in order to enable petrol attendants.

  13. Partial oxidation of jet fuels over Rh/Al_2O_3. Design and reaction kinetics of sulfur-containing surrogates

    International Nuclear Information System (INIS)

    Baer, Julian Nicolaas

    2016-01-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al_2O_3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al_2O_3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An

  14. A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

    KAUST Repository

    Raj, Abhijeet; Charry Prada, Iran David; Amer, Ahmad Amer; Chung, Suk-Ho

    2012-01-01

    This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline

  15. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  16. Reaction of active uranium and thorium with aromatic carbonyls and pinacols in hydrocarbon solvents

    International Nuclear Information System (INIS)

    Kahn, B.E.; Rieke, R.D.

    1988-01-01

    Highly reactive uranium and thorium metal powders have been prepared by reduction of the anhydrous metal(IV) chlorides in hydrocarbon solvents. The reduction employs the crystalline hydrocarbon-soluble reducing agent [(TMEDA)Li] 2 [Nap] (TMEDA = N,N,N',N'-tetramethylethylenediamine, Nap = naphthalene). The resulting active metal powders have been shown to be extremely reactive with oxygen-containing compounds and have been used in the reductive coupling of aromatic ketones giving tetra-arylethylenes. Reactions with pinacols have given some mechanistic insight into the ketone coupling reaction. These finely divided metal powders activate very weakly acidic C-H bonds forming metal hydrides, which can be transferred to organic substrates

  17. Activated carbon as catalyst for microwave-assisted wet peroxide oxidation of aromatic hydrocarbons.

    Science.gov (United States)

    Garcia-Costa, Alicia L; Lopez-Perela, Lucia; Xu, Xiyan; Zazo, Juan A; Rodriguez, Juan J; Casas, Jose A

    2018-05-21

    This paper addresses the removal of four aromatic hydrocarbons typically found in petrochemical wastewater: benzene (B), toluene (T), o-xylene (X), and naphthalene (N), by microwave-assisted catalytic wet peroxide oxidation (MW-CWPO) using activated carbon (AC) as catalyst. Under the studied conditions, complete pollutant elimination (B, 1.28 mM; T, 1.09 mM; X, 0.94 mM; and N, 0.78 mM) was achieved, with more than 90% TOC removal after only 15-min reaction time, working at 120 °C, pH 0  = 3, AC at 1 g L -1 , and H 2 O 2 at the stoichiometric dose. Furthermore, in the case of toluene, naphthalene, and xylene, the hydroxylation and breakdown of the ring is very rapid and toxic intermediates were not detected. The process follows two steps: (i) pollutant adsorption onto AC followed by (ii) adsorbed compounds oxidation. Thus, MW-CWPO with AC as catalyst appears a promising way for a fast and effective process for B, T, X, and N removal in aqueous phase.

  18. Partial Oxidation of High-Boiling Hydrocarbon Mixtures in the Pilot Unit

    Czech Academy of Sciences Publication Activity Database

    Hanika, Jiří; Lederer, J.; Nečesaný, F.; Poslední, W.; Tukač, V.; Veselý, Václav

    2014-01-01

    Roč. 68, č. 12 (2014), s. 1701-1706 ISSN 0366-6352 Institutional support: RVO:67985858 Keywords : partial oxidation * high-boiling hydrocarbons * pilot plant Subject RIV: CI - Industrial Chemistry , Chemical Engineering Impact factor: 1.468, year: 2014

  19. Pulse radiolysis of alkanes in the gas-phase, ion-molecule reactions and neutralization mechanisms of hydrocarbon ions

    International Nuclear Information System (INIS)

    Ausloos, P.

    1975-01-01

    A discussion is presented of the fate of unreactive hydrocarbon ions in various selected gaseous systems. It is shown that experiments performed with the high radiation dose rates obtained in pulse radiolysis experiments have several advantages over conventional low dose rate experiments for the elucidation of the mechanism of homogeneous neutralization of unreactive hydrocarbon ions. This is so because the charged species has a much shorter lifetime with respect to neutralization under high dose rate (pulse radiolysis) conditions, so that the reaction of the ions with minor impurities or accumulated products is much less probable than in low dose rate experiments. It is further shown through a few examples, that quantitative information about the rate contants of neutralization events and ion-molecule reactions can be obtained when the dose rate is high enough for neutralization and chemical reaction to be in competition. Once reliable rate constants for neutralization and ion-molecule reactions are derived, one can obtain a quantitative evaluation of the products which will by formed in the pulse radiolysis of a hydrocarbon gas mixture from a computer calculation. (author)

  20. Sputtering yields and surface chemical modification of tin-doped indium oxide in hydrocarbon-based plasma etching

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hu; Karahashi, Kazuhiro; Hamaguchi, Satoshi, E-mail: hamaguch@ppl.eng.osaka-u.ac.jp [Center for Atomic and Molecular Technologies, Osaka University, Yamadaoka 2-1, Suita 565-0871 (Japan); Fukasawa, Masanaga; Nagahata, Kazunori; Tatsumi, Tetsuya [Device and Material R& D Group, RDS Platform, Sony Corporation, Kanagawa 243-0014 (Japan)

    2015-11-15

    Sputtering yields and surface chemical compositions of tin-doped indium oxide (or indium tin oxide, ITO) by CH{sup +}, CH{sub 3}{sup +}, and inert-gas ion (He{sup +}, Ne{sup +}, and Ar{sup +}) incidence have been obtained experimentally with the use of a mass-selected ion beam system and in-situ x-ray photoelectron spectroscopy. It has been found that etching of ITO is chemically enhanced by energetic incidence of hydrocarbon (CH{sub x}{sup +}) ions. At high incident energy incidence, it appears that carbon of incident ions predominantly reduce indium (In) of ITO and the ITO sputtering yields by CH{sup +} and CH{sub 3}{sup +} ions are found to be essentially equal. At lower incident energy (less than 500 eV or so), however, a hydrogen effect on ITO reduction is more pronounced and the ITO surface is more reduced by CH{sub 3}{sup +} ions than CH{sup +} ions. Although the surface is covered more with metallic In by low-energy incident CH{sub 3}{sup +} ions than CH{sup +} ions and metallic In is in general less resistant against physical sputtering than its oxide, the ITO sputtering yield by incident CH{sub 3}{sup +} ions is found to be lower than that by incident CH{sup +} ions in this energy range. A postulation to account for the relation between the observed sputtering yield and reduction of the ITO surface is also presented. The results presented here offer a better understanding of elementary surface reactions observed in reactive ion etching processes of ITO by hydrocarbon plasmas.

  1. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian

    2004-07-01

    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  2. Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Allen, Wesley D. [University of Georgia, Department of Chemistry and Center for Computational Quantum Chemistry; Schaefer, Henry F. [University of Georgia, Center for Computational Quantum Chemistry

    2018-04-08

    The research program supported by this DOE grant carried out both methodological development and computational applications of first-principles theoretical chemistry based on quantum mechanical wavefunctions, as directed toward understanding and harnessing the fundamental chemical physics of combustion. To build and refine the world’s database of thermochemistry, spectroscopy, and chemical kinetics, predictive and definitive computational methods are needed that push the envelope of modern electronic structure theory. The application of such methods has been made to gain comprehensive knowledge of the paradigmatic reaction networks by which the n- and i-propyl, t-butyl, and n-butyl radicals are oxidized by O2. Numerous ROO and QOOH intermediates in these R + O2 reaction systems have been characterized along with the interconnecting isomerization transition states and the barriers leading to fragmentation. Other combustion-related intermediates have also been studied, including methylsulfinyl radical, cyclobutylidene, and radicals derived from acetaldehyde and vinyl alcohol. Theoretical advances have been achieved and made available to the scientific community by implementation into PSI4, an open-source electronic structure computer package emphasizing automation, advanced libraries, and interoperability. We have pursued the development of universal explicitly correlated methods applicable to general electronic wavefunctions, as well as a framework that allows multideterminant reference functions to be expressed as a single determinant from quasiparticle operators. Finally, a rigorous analytical tool for correlated wavefunctions has been created to elucidate dispersion interactions, which play essential roles in many areas of chemistry, but whose effects are often masked and enigmatic. Our research decomposes and analyzes the coupled-cluster electron correlation energy in molecular systems as a function of interelectronic distance. Concepts

  3. Tuning functionality of photocatalytic materials: an infrared study on hydrocarbon oxidation

    NARCIS (Netherlands)

    Amrollahi Buky, Rezvaneh

    2016-01-01

    The focus of the research described in this thesis was on the engineering and design of effective photocatalysts able to catalyze the oxidative conversion of hydrocarbons. The prepared catalysts were synthesized by using different procedures involving sol gel precursors, and impregnation or

  4. Partial oxidation of jet fuels over Rh/Al{sub 2}O{sub 3}. Design and reaction kinetics of sulfur-containing surrogates

    Energy Technology Data Exchange (ETDEWEB)

    Baer, Julian Nicolaas

    2016-07-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al{sub 2}O{sub 3} at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al{sub 2}O{sub 3}, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product

  5. Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

    International Nuclear Information System (INIS)

    Westbrook, C.K.

    2000-01-01

    Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignition in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical combustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant. However, there are many combustion factors that can influence these two major reactions, and these are the features that vary from one practical system to another

  6. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  7. Hydrogenating gaseous hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nicolardot, P L.F.

    1930-08-06

    Gaseous hydrocarbons obtained by the destructive distillation of carbonaceous materials are simultaneously desulfurized and hydrogenated by passing them at 350 to 500/sup 0/C, mixed with carbon monoxide and water vapor over lime mixed with metallic oxides present in sufficient amount to absorb the carbon dioxide as it is formed. Oxides of iron, copper, silver, cobalt, and metals of the rare earths may be used and are mixed with the lime to form a filling material of small pieces filling the reaction vessel which may have walls metallized with copper and zinc dust. The products are condensed and fixed with absorbents, e.g. oils, activated carbon, silica gels. The metallic masses may be regenerated by a hot air stream and by heating in inert gases.

  8. Optimization of operating conditions in oxidation of dibenzothiophene in the light hydrocarbon model

    Directory of Open Access Journals (Sweden)

    Akbari Azam

    2014-01-01

    Full Text Available In this research, the effects of process variables on the efficiency and mechanism of dibenzothiophene oxidation in formicacid/H2O2 system for deep desulfurization of a light hydrocarbon model were systematically studied by statistical modelling and optimization using response surface methodology and implementing the central composite design. A quadratic regression model was developed to predict the yield of sulfur oxidation as the model response. The model indicated that temperature was the most significant effective factor and suggested an important interaction between temperature and H2O2/sulfur ratio; at temperatures above 56°C, more excess oxidant was necessary because of instability of active peroxo intermediates and loss of H2O2 due to thermal decomposition. In contrast, the water hindrance effect of H2O2 aqueous solution in desulfurization progress was more significant at temperatures bellow 56°C. In the optimization process, minimizing H2O2/sulfur ratio and catalyst consumption for maximum yield of desulfurization was economically considerable. The optimal condition was obtained at temperature of 57 °C, H2O2/sulfur ratio of 2.5 mol/mol and catalyst dosage of 0.82 mL in 50 mL solution of DBT in n-hexane leading to a maximum oxidation yield of 95% after 1 hour reaction. Good agreement between predicted and experimental results (less than 4% error was found.

  9. Hydrocarbon fuel processing of micro solid oxide fuel cell systems[Dissertation 17455

    Energy Technology Data Exchange (ETDEWEB)

    Stutz, M. J.

    2007-07-01

    The scope of this thesis is the numerical and experimental investigation of the fuel processing of a micro solid oxide fuel cell (SOFC) running on hydrocarbon fuel. The goal is to enhance the overall system efficiency by optimization of the reforming process in the steady state and the improvement of the start-up process. Micro SOFC are a potential alternative to the currently used batteries in portable devices. Liquid butane in a cartridge could be the energy source. This dissertation is focused on the fuel processing of the system, namely the reforming and post-combusting processes. The reformer converts the hydrocarbon fuel to a hydrogen rich gas that can be utilized by the SOFC. The post-combustor depletes the toxic and/or explosive gases before leaving the exhaust. Chapter One presents a short introduction to the field of hydrocarbon fuel processing in micro solid oxide fuel cell systems, the next three chapters deal with computational modeling of the transport phenomena inside a micro-reformer, which leads to a better understanding of the chemistry and the physics therein, hence progress in the design and operation parameters. The experimental part (i.e. Chapter Five) of this thesis focuses on the feasibility of a novel hybrid start-up method of a fuel cell system that employs existing components as an additional heat source. In Chapter Two the effect of wall heat conduction on the syngas (hydrogen and carbon monoxide) production of a micro-reformer, representing micro-fabricated channels or monoliths, is investigated. Methane is used as a model hydrocarbon fuel since its heterogeneous reaction path on rhodium is known and validated. The simulations demonstrate that the axial wall conduction strongly influences the performance of the micro-reformer and should not be neglected without a careful a priori investigation of its impact. Methane conversion and hydrogen yield are strongly dependent of the wall inner surface temperature, which is influenced by the

  10. Catalysts for the production of hydrocarbons from carbon monoxide and water

    Science.gov (United States)

    Sapienza, R.S.; Slegeir, W.A.; Goldberg, R.I.

    1985-11-06

    A method of converting low H/sub 2//CO ratio syngas to carbonaceous products comprising reacting the syngas with water or steam at 200 to 350/sup 0/C in the presence of a metal catalyst supported on zinc oxide. Hydrocarbons are produced with a catalyst selected from cobalt, nickel or ruthenium and alcohols are produced with a catalyst selected from palladium, platinum, ruthenium or copper on the zinc oxide support. The ratio of the reactants are such that for alcohols and saturated hydrocarbons: (2n + 1) greater than or equal to x greater than or equal to O and for olefinic hydrocarbons: 2n greater than or equal to x greater than or equal to O where n is the number of carbon atoms in the product and x is the molar amount of water in the reaction mixture.

  11. Integrated process using non-stoichiometric sulfides or oxides of potassium for making less active metals and hydrocarbons

    International Nuclear Information System (INIS)

    Swanson, R.

    1984-01-01

    Disclosed is a combinative integrated chemical process using inorganic reactants and yielding, if desired, organic products. The process involves first the production of elemental potassium by the thermal or thermal-reduced pressure decomposition of potassium oxide or potassium sulfide and distillation of the potassium. This elemental potassium is then used to reduce ores or ore concentrates of copper, zinc, lead, magnesium, cadmium, iron, arsenic, antimony or silver to yield one or more of these less active metals in elemental form. Process potassium can also be used to produce hydrogen by reaction with water or potassium hydroxide. This hydrogen is reacted with potassium to produce potassium hydride. Heating the latter with carbon produces potassium acetylide which forms acetylene when treated with water. Acetylene is hydrogenated to ethene or ethane with process hydrogen. Using Wurtz-Fittig reaction conditions, the ethane can be upgraded to a mixture of hydrocarbons boiling in the fuel range

  12. Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

    Energy Technology Data Exchange (ETDEWEB)

    Buss, R.J.; Baseman, R.J.; Guozhong, H.; Lee, Y.T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  13. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    Science.gov (United States)

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  14. Methods for forming complex oxidation reaction products including superconducting articles

    International Nuclear Information System (INIS)

    Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

    1992-01-01

    This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

  15. Magnetic graphene oxide as adsorbent for the determination of polycyclic aromatic hydrocarbon metabolites in human urine.

    Science.gov (United States)

    Zhu, Linli; Xu, Hui

    2014-09-01

    Detection of monohydroxy polycyclic aromatic hydrocarbons metabolites in urine is an advisable and valid method to assess human environmental exposure to polycyclic aromatic hydrocarbons. In this work, novel Fe3O4/graphene oxide composites were prepared and their application in the magnetic solid-phase extraction of monohydroxy polycyclic aromatic hydrocarbons in urine was investigated by coupling with liquid chromatography and mass spectrometry. In the hybrid material, superparamagnetic Fe3O4 nanoparticles provide fast separation to simplify the analytical process and graphene oxide provides a large functional surface for the adsorption. The prepared magnetic nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometry. The experimental conditions were optimized systematically. Under the optimal conditions, the recoveries of these compounds were in the range of 98.3-125.2%, the relative standard deviations ranged between 6.8 and 15.5%, and the limits of detection were in the range of 0.01-0.15 ng/mL. The simple, quick, and affordable method was successfully used in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities. The results indicated that the monohydroxy polycyclic aromatic hydrocarbons level in human urine can provide useful information for environmental exposure to polycyclic aromatic hydrocarbons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The effect of prolonged flooding of an oil deposit on the special composition and the activity of hydrocarbon-oxidizing microflora

    Energy Technology Data Exchange (ETDEWEB)

    Berdichevskaya, M V

    1982-07-01

    The special composition of hydrocarbon-oxidizing bacteria was studied in terrigenous and carbonate oil-bearing strata from several deposits of the Permian Cis-Ural region. We isolated 43 strains and assigned them to the following genera: Mycobacterium, Micrococcus, Brevibacterium, Corynebacterium, Flavobacterium, Achromobacter and Pseudomonas. The special composition of the hydrocarbon-oxidizing microflora was shown to depend on the flooding of an oil stratum, as a result of which the ecological environment in a deposit changed. Gram-positive coryneform bacteria were found in stratal salinized waters and in diluted stratal waters. Gram-negative hydrocarbon-oxidizing bacteria were isolated from pumped-in river waters and from stratal waters diluted by 70-100% as the result of flooding. The metabolic activity of Corynebacterium fascians (2 strains), Mycobacterium rubrum (1 strain), Pseudomonas mira (1 strain) and Flavobacterium perigrinum (1 strain) was assayed in stratal waters with different concentrations of salts. The coryneform hydrocarbon-oxidizing bacteria were shown to be very halotolerant as the result of adaptation; that is why the incidence of these microorganisms is very great in highly mineralized stratal water of oil deposits.

  17. Studies of Catalytic Properties of Inorganic Rock Matrices in Redox Reactions

    Directory of Open Access Journals (Sweden)

    Nikolay M. Dobrynkin

    2017-09-01

    Full Text Available Intrinsic catalytic properties of mineral matrices of various kinds (basalts, clays, sandstones were studied, which are of interest for in-situ heavy oil upgrading (i.e., underground to create advanced technologies for enhanced oil recovery. The elemental, surface and phase composition and matrix particle morphology, surface and acidic properties were studied using elemental analysis, X-ray diffraction, adsorption and desorption of nitrogen and ammonia. The data on the catalytic activity of inorganic matrices in ammonium nitrate decomposition (reaction with a large gassing, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltenes into maltenes (the conversion of heavy hydrocarbons into more valuable light hydrocarbons were discussed. In order to check their applicability for the asphaltenes hydrocracking catalytic systems development, basalt and clay matrices were used as supports for iron/basalt, nickel/basalt and iron/clay catalysts. The catalytic activity of the matrices in the reactions of the decomposition of ammonium nitrate, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltens was observed for the first time.

  18. Hydrogen addition reactions of aliphatic hydrocarbons in comets

    Science.gov (United States)

    Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H.

    2013-10-01

    Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.

  19. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  20. Fractional separation of hydrocarbon vapours

    Energy Technology Data Exchange (ETDEWEB)

    1937-07-10

    A process is described for converting higher boiling hydrocarbons to lower boiling hydrocarbons by subjecting them at elevated temperatures to a conversion operation, then separating the higher and lower boiling fractions. The separation takes place while the reaction products are maintained in the vapor phase by contact with a mass of solid porous material which has little or no catalytic activity but does have a preferential absorption property for higher boiling hydrocarbons so that the lower boiling part of the reaction products pass through the separation zone while the heavier hydrocarbons are retained. The separation is accomplished without substantial loss of heat of these reaction products.

  1. Halogen-Mediated Conversion of Hydrocarbons to Commodities.

    Science.gov (United States)

    Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

    2017-03-08

    Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

  2. Low temperature removal of surface oxides and hydrocarbons from Ge(100) using atomic hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Walker, M., E-mail: m.walker@warwick.ac.uk; Tedder, M.S.; Palmer, J.D.; Mudd, J.J.; McConville, C.F.

    2016-08-30

    Highlights: • Preparation of a clean, well-ordered Ge(100) surface with atomic hydrogen. • Surface oxide layers removed by AHC at room temperature, but not hydrocarbons. • Increasing surface temperature during AHC dramatically improves efficiency. • AHC with the surface heated to 250 °C led to a near complete removal of contaminants. • (2 × 1) LEED pattern from IBA and AHC indicates asymmetric dimer reconstruction. - Abstract: Germanium is a group IV semiconductor with many current and potential applications in the modern semiconductor industry. Key to expanding the use of Ge is a reliable method for the removal of surface contamination, including oxides which are naturally formed during the exposure of Ge thin films to atmospheric conditions. A process for achieving this task at lower temperatures would be highly advantageous, where the underlying device architecture will not diffuse through the Ge film while also avoiding electronic damage induced by ion irradiation. Atomic hydrogen cleaning (AHC) offers a low-temperature, damage-free alternative to the common ion bombardment and annealing (IBA) technique which is widely employed. In this work, we demonstrate with X-ray photoelectron spectroscopy (XPS) that the AHC method is effective in removing surface oxides and hydrocarbons, yielding an almost completely clean surface when the AHC is conducted at a temperature of 250 °C. We compare the post-AHC cleanliness and (2 × 1) low energy electron diffraction (LEED) pattern to that obtained via IBA, where the sample is annealed at 600 °C. We also demonstrate that the combination of a sample temperature of 250 °C and atomic H dosing is required to clean the surface. Lower temperatures prove less effective in removal of the oxide layer and hydrocarbons, whilst annealing in ultra-high vacuum conditions only removes weakly bound hydrocarbons. Finally, we examine the subsequent H-termination of an IBA-cleaned sample using XPS, LEED and ultraviolet

  3. Hydrocarbon-degrading sulfate-reducing bacteria in marine hydrocarbon seep sediments

    OpenAIRE

    Kleindienst, Sara

    2012-01-01

    Microorganisms are key players in our biosphere because of their ability to degrade various organic compounds including a wide range of hydrocarbons. At marine hydrocarbon seeps, more than 90% of sulfate reduction (SR) is potentially coupled to non-methane hydrocarbon oxidation. Several hydrocarbon-degrading sulfate-reducing bacteria (SRB) were enriched or isolated from marine sediments. However, in situ active SRB remained largely unknown. In the present thesis, the global distribution and a...

  4. Solution mining and heating by oxidation for treating hydrocarbon containing formations

    Science.gov (United States)

    Vinegar, Harold J.; Stegemeier, George Leo

    2009-06-23

    A method for treating an oil shale formation comprising nahcolite includes providing a first fluid to a portion of the formation. A second fluid is produced from the portion. The second fluid includes at least some nahcolite dissolved in the first fluid. A controlled amount of oxidant is provided to the portion of the formation. Hydrocarbon fluids are produced from the formation.

  5. Targeting of insect epicuticular lipids by the entomopathogenic fungus Beauveria bassiana: hydrocarbon oxidation within the context of a host-pathogen interaction

    Science.gov (United States)

    Pedrini, Nicolás; Ortiz-Urquiza, Almudena; Huarte-Bonnet, Carla; Zhang, Shizhu; Keyhani, Nemat O.

    2013-01-01

    Broad host range entomopathogenic fungi such as Beauveria bassiana attack insect hosts via attachment to cuticular substrata and the production of enzymes for the degradation and penetration of insect cuticle. The outermost epicuticular layer consists of a complex mixture of non-polar lipids including hydrocarbons, fatty acids, and wax esters. Long chain hydrocarbons are major components of the outer waxy layer of diverse insect species, where they serve to protect against desiccation and microbial parasites, and as recognition molecules or as a platform for semiochemicals. Insect pathogenic fungi have evolved mechanisms for overcoming this barrier, likely with sets of lipid degrading enzymes with overlapping substrate specificities. Alkanes and fatty acids are substrates for a specific subset of fungal cytochrome P450 monooxygenases involved in insect hydrocarbon degradation. These enzymes activate alkanes by terminal oxidation to alcohols, which are further oxidized by alcohol and aldehyde dehydrogenases, whose products can enter β-oxidation pathways. B. bassiana contains at least 83 genes coding for cytochrome P450s (CYP), a subset of which are involved in hydrocarbon oxidation, and several of which represent new CYP subfamilies/families. Expression data indicated differential induction by alkanes and insect lipids and four CYP proteins have been partially characterized after heterologous expression in yeast. Gene knockouts revealed a phenotype for only one (cyp52X1) out of six genes examined to date. CYP52X1 oxidizes long chain fatty acids and participates in the degradation of specific epicuticular lipid components needed for breaching the insect waxy layer. Examining the hydrocarbon oxidizing CYP repertoire of pathogens involved in insect epicuticle degradation can lead to the characterization of enzymes with novel substrate specificities. Pathogen targeting may also represent an important co-evolutionary process regarding insect cuticular hydrocarbon

  6. GAS-PHASE REACTIONS OF POLYCYCLIC AROMATIC HYDROCARBON ANIONS WITH MOLECULES OF INTERSTELLAR RELEVANCE

    International Nuclear Information System (INIS)

    Demarais, Nicholas J.; Yang Zhibo; Martinez, Oscar; Wehres, Nadine; Bierbaum, Veronica M.; Snow, Theodore P.

    2012-01-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C 6 H – 5 ), naphthalenide (C 10 H – 7 ), and anthracenide (C 14 H – 9 ) with atomic H, H 2 , and D 2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O 2 , CO 2 , N 2 O, C 2 H 2 , CH 3 OH, CH 3 CN, (CH 3 ) 2 CO, CH 3 CHO, CH 3 Cl, and (CH 3 CH 2 ) 2 O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  7. Gas-phase Reactions of Polycyclic Aromatic Hydrocarbon Anions with Molecules of Interstellar Relevance

    Science.gov (United States)

    Demarais, Nicholas J.; Yang, Zhibo; Martinez, Oscar; Wehres, Nadine; Snow, Theodore P.; Bierbaum, Veronica M.

    2012-02-01

    We have studied reactions of small dehydrogenated polycyclic aromatic hydrocarbon anions with neutral species of interstellar relevance. Reaction rate constants are measured at 300 K for the reactions of phenide (C6H- 5), naphthalenide (C10H- 7), and anthracenide (C14H- 9) with atomic H, H2, and D2 using a flowing afterglow-selected ion flow tube instrument. Reaction rate constants of phenide with neutral molecules (CO, O2, CO2, N2O, C2H2, CH3OH, CH3CN, (CH3)2CO, CH3CHO, CH3Cl, and (CH3CH2)2O) are also measured under the same conditions. Experimental measurements are accompanied by ab initio calculations to provide insight into reaction pathways and enthalpies. Our measured reaction rate constants should prove useful in the modeling of astrophysical environments, particularly when applied to dense regions of the interstellar and circumstellar medium.

  8. Oxidation reactions of bilirubin in aqueous solutions

    International Nuclear Information System (INIS)

    Mohan, Hari; Gopinathan, C.

    1990-01-01

    The radical cation of bilirubin (BR) has been tentatively identified as a transient intermediate in the reactions of BR with different oxidizing species such as Br 2 - , I 2 - and CH 3 I . OH. The rate constants for these reactions have been determined as 2.4 x 10 9 , l.0 x 10 9 and 2.7 x 10 9 dm 3 mol -1 s -1 , respectively. Biliverdin is likely to be among the stable products formed on oxidation of BR by these oxidizing species. (author)

  9. Reaction between vanadium trichloride oxide and hydrogen sulfide

    International Nuclear Information System (INIS)

    Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

    1978-01-01

    The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

  10. Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

    Science.gov (United States)

    Jiang, Huanhuan; Jang, Myoseon; Yu, Zechen

    2017-08-01

    When hydrocarbons (HCs) are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs). These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes) and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs) to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t = 30 min) of dithiothreitol (DTTt), a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2-5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC / NOx ratio from 30 to 5). The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm) was determined over an extended period of reaction time (t = 2 h) to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC / NOx ratio: 5-36 ppbC ppb-1) applied in this study, the amount of organic hydroperoxides was

  11. New Insights into the Diels-Alder Reaction of Graphene Oxide.

    Science.gov (United States)

    Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

    2016-04-18

    Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    Science.gov (United States)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  13. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    Science.gov (United States)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  14. Microplasma reforming of hydrocarbons for fuel cell power

    Science.gov (United States)

    Besser, R. S.; Lindner, P. J.

    The implementation of a microplasma approach for small scale reforming processes is explored as an alternative to more standard catalyst-based processes. Plasmas are a known approach to activating a chemical reaction in place of catalysts, and microplasmas are particularly attractive owing to their extremely high electron and power densities. Their inherent compactness gives them appeal for portable applications, but their modularity leads to scalability for higher capacity. We describe the realization of experimental microplasma reactors based on the microhollow cathode discharge (MHCD) structure by silicon micromachining for device fabrication. Experiments were carried out with model hydrocarbons methane and butane in the reactors within a microfluidic flow and analytical setup. We observe several key phenomena, including the ability to liberate hydrogen from the hydrocarbons at temperatures near ambient and sub-Watt input power levels, the tendency toward hydrocarbon decomposition rather than oxidation even in the presence of oxygen, and the need for a neutral carrier to obtain conversion. Mass and energy balances on these experiments revealed conversions up to nearly 50%, but the conversion of electrical power input to chemical reaction enthalpy was only on the order of 1%. These initial, exploratory results were recorded with devices and at process settings without optimization, and are hence promising for an emerging, catalyst-free reforming approach.

  15. Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xuejiao; XU Liangyou

    2017-01-01

    Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

  16. Synthesis of extended polycyclic aromatic hydrocarbons by oxidative tandem spirocyclization and 1,2-aryl migration

    Science.gov (United States)

    Zhang, Xuan; Xu, Zhanqiang; Si, Weili; Oniwa, Kazuaki; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan

    2017-04-01

    The extended polycyclic aromatic hydrocarbons (PAHs) have received significant interdisciplinary attention due to their semiconducting applications in diverse organic electronics as well as intriguing structural interests of well-defined graphene segments. Herein, a highly efficient oxidative spirocyclization and 1,2-aryl migration tandem synthetic method for the construction of extended polyaromatic hydrocarbons (PAHs) has been developed. The CuCl-catalyst/PhCO3 tBu or DDQ oxidation system in the presence of trifluoroacetic acid enables the selective single-electron oxidation to take place preferentially at the more electron-rich alkene moiety of o-biphenylyl-substituted methylenefluorenes, giving rise to the subsequent tandem process. A variety of structurally diverse extended PAHs including functionalized dibenzo[g,p]chrysenes, benzo[f]naphtho[1,2-s]picene, hexabenzo[a,c,fg,j,l,op]tetracene, tetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene, tetrabenzo[a,c,f,k]phenanthro[9,10-m]tetraphene, tetrabenzo[a,c,f,o]phenanthro[9,10-m]picene and S-type helicene have been readily synthesized.

  17. Method of preparing and utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream

    Science.gov (United States)

    Berry, David A; Shekhawat, Dushyant; Smith, Mark; Haynes, Daniel

    2013-07-16

    The disclosure relates to a method of utilizing a catalyst system for an oxidation process on a gaseous hydrocarbon stream with a mitigation of carbon accumulation. The system is comprised of a catalytically active phase deposited onto an oxygen conducting phase, with or without supplemental support. The catalytically active phase has a specified crystal structure where at least one catalytically active metal is a cation within the crystal structure and coordinated with oxygen atoms within the crystal structure. The catalyst system employs an optimum coverage ratio for a given set of oxidation conditions, based on a specified hydrocarbon conversion and a carbon deposition limit. Specific embodiments of the catalyst system are disclosed.

  18. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    International Nuclear Information System (INIS)

    Janev, R.K.; Kato, T.; Wang, J.G.

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  19. Rate constants for the reaction of CF3O radicals with hydrocarbons at 298 K

    DEFF Research Database (Denmark)

    Kelly, C.; Treacy, J.; Sidebottom, H.W.

    1993-01-01

    Rate constant ratios of the reactions of CF3O radicals with a number of hydrocarbons have been determined at 298 +/- 2 K and atmospheric pressure using a relative rate method. Using a previously determined value k(CF30 + C2H6) = 1.2 x 10(-12) cm3 molecule-1 s-1 these rate constant ratios provide...... estimates of the rate constants: k(CF3O + CH4) = (1.2 +/- 0.1) x 10(-14), k(CF3O + c-C3H6) = (3.6 +/- 0.2) x 10(-13), k(CF3O + C3H8) = (4.7 +/- 0.7) x 10(-12), k(CF3O + (CH3)3CH) = (7.2 +/- 0.5) x 10(-12), k(CF3O + C2H4) = (3.0 +/- 0.1) x 10(-11) and k(CF3O + C6H6) = (3.6 +/- 0.1) x 10(-11) cm3 molecule-1 s......-1. The importance of the reactions of CF3O radicals with hydrocarbons under atmospheric conditions is discussed....

  20. Optrode for sensing hydrocarbons

    Science.gov (United States)

    Miller, H.; Milanovich, F.P.; Hirschfeld, T.B.; Miller, F.S.

    1988-09-13

    A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons. 5 figs.

  1. Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

    Directory of Open Access Journals (Sweden)

    H. Jiang

    2017-08-01

    Full Text Available When hydrocarbons (HCs are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs. These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t =  30 min of dithiothreitol (DTTt, a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2–5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC ∕ NOx ratio from 30 to 5. The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm was determined over an extended period of reaction time (t =  2 h to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC ∕ NOx ratio: 5–36 ppbC ppb−1 applied in

  2. Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

    Science.gov (United States)

    Liwosz, Timothy W; Chemler, Sherry R

    2013-06-21

    We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

  3. Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

    2001-05-01

    The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

  4. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

  5. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Sugiura, Toshio.

    1977-01-01

    The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

  6. Method of removing deterioration product in hydrocarbon type solvent

    International Nuclear Information System (INIS)

    Ito, Yoshifumi; Takashina, Toru; Murasawa, Kenji.

    1988-01-01

    Purpose: To remarkably reduce radioactive wastes by bringing adsorbents comprising titanium oxide and/or zirconium oxide into contact with hydrocarbon type solvents. Method: In a nuclear fuel re-processing step, an appropriate processing is applied to extraction solvents suffering from radioactive degradation, to separate the hydrocarbon solvents and store them in a solvent tank. Then, titanium oxide and/or zirconium oxide adsorbents are continuously mixed and agitated therewith to adsorb degradation products on the adsorbents. Then, they are introduced with adsorbent separators to recover purified hydrocarbon type solvents. Meanwhile, the separated adsorbents are discharged from pipeways. This enables to regenerate the hydrocarbon type solvents for reuse, as well as remarkably reduce the radioactive wastes. (Takahashi, M.)

  7. Deep catalytic oxidation of heavy hydrocarbons on Pt/Al{sub 2}O{sub 3} catalysts; Oxydation catalytique totale des hydrocarbures lourds sur Pt/Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Diehl, F.

    1998-12-09

    Deep oxidation by air on Pt supported on alumina of a large number of heavy hydrocarbons representative of those found in a real Diesel car exhaust has been studied. Light-off temperatures between 140 and 320 deg. C on 1%Pt/alumina (80% metal dispersion) have been found. Results show that not only the physical state around the conversion area but also the chemical nature of the hydrocarbon plays an important role. Heavy hydrocarbons deep oxidation behaviour has been classified as a function of their chemical category (alkane, alkene, aromatics etc..). Oxidation of binary mixtures of hydrocarbons has shown strong inhibition effects on n-alkane or CO oxidation by polycyclic compounds like 1-methyl-naphthalene. In some cases, by-product compounds in the gas effluent (other than CO{sub 2} and H{sub 2}O) have been identified by mass-spectrometry leading to oxidation mechanism proposals for different hydrocarbons. Catalyst nature (metal dispersion, content) influence has also been studied. It is shown that turn-over activity is favoured by the increase of the metal bulk size. Acidity influence of the carrier has shown only very little influence on n-alkane or di-aromatic compound oxidation. (author)

  8. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  9. Identification of novel methane-, ethane-, and propane-oxidizing bacteria at marine hydrocarbon seeps by stable isotope probing.

    Science.gov (United States)

    Redmond, Molly C; Valentine, David L; Sessions, Alex L

    2010-10-01

    Marine hydrocarbon seeps supply oil and gas to microorganisms in sediments and overlying water. We used stable isotope probing (SIP) to identify aerobic bacteria oxidizing gaseous hydrocarbons in surface sediment from the Coal Oil Point seep field located offshore of Santa Barbara, California. After incubating sediment with (13)C-labeled methane, ethane, or propane, we confirmed the incorporation of (13)C into fatty acids and DNA. Terminal restriction fragment length polymorphism (T-RFLP) analysis and sequencing of the 16S rRNA and particulate methane monooxygenase (pmoA) genes in (13)C-DNA revealed groups of microbes not previously thought to contribute to methane, ethane, or propane oxidation. First, (13)C methane was primarily assimilated by Gammaproteobacteria species from the family Methylococcaceae, Gammaproteobacteria related to Methylophaga, and Betaproteobacteria from the family Methylophilaceae. Species of the latter two genera have not been previously shown to oxidize methane and may have been cross-feeding on methanol, but species of both genera were heavily labeled after just 3 days. pmoA sequences were affiliated with species of Methylococcaceae, but most were not closely related to cultured methanotrophs. Second, (13)C ethane was consumed by members of a novel group of Methylococcaceae. Growth with ethane as the major carbon source has not previously been observed in members of the Methylococcaceae; a highly divergent pmoA-like gene detected in the (13)C-labeled DNA may encode an ethane monooxygenase. Third, (13)C propane was consumed by members of a group of unclassified Gammaproteobacteria species not previously linked to propane oxidation. This study identifies several bacterial lineages as participants in the oxidation of gaseous hydrocarbons in marine seeps and supports the idea of an alternate function for some pmoA-like genes.

  10. Selective Synthesis of Gasoline-Ranged Hydrocarbons from Syngas over Hybrid Catalyst Consisting of Metal-Loaded ZSM-5 Coupled with Copper-Zinc Oxide

    Directory of Open Access Journals (Sweden)

    Ting Ma

    2014-04-01

    Full Text Available The conversion of syngas (CO + H2 to gasoline-ranged hydrocarbons was carried out using a hybrid catalyst consisting of metal-loaded ZSM-5 coupled with Cu-ZnO in a near-critical n-hexane solvent. Methanol was synthesized from syngas over Cu-ZnO; subsequently, was converted to hydrocarbons through the formation of dimethyl ether (DME over the metal-loaded ZSM-5. When 0.5 wt% Pd/ZSM-5 and 5 wt% Cu/ZSM-5 among the metal-loaded ZSM-5 catalysts with Pd, Co, Fe or Cu were employed as a portion of the hybrid catalyst, the gasoline-ranged hydrocarbons were selectively produced (the gasoline-ranged hydrocarbons in all hydrocarbons: 59% for the hybrid catalyst with Pd/ZSM-5 and 64% for that with Cu/ZSM-5 with a similar CO conversion during the reaction. An increase in the Cu loading on ZSM-5 resulted in increasing the yield of the gasoline-ranged hydrocarbons, and in decreasing the yield of DME. Furthermore, the hybrid catalyst with Cu/ZSM-5 exhibited no deactivation for 30 h of the reaction. It was revealed that a hybrid catalyst containing Cu/ZSM-5 was efficient in the selective synthesis of gasoline-ranged hydrocarbons from syngas via methanol in the near-critical n-hexane fluid.

  11. Graphene oxide-mediated rapid dechlorination of carbon tetrachloride by green rust

    DEFF Research Database (Denmark)

    Huang, Li-Zhi; Hansen, Hans Christian B.; Daasbjerg, Kim

    2017-01-01

    Graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of chlorinated aliphatic hydrocarbons. In this study as low amounts as ∼0.007 % of graphene oxide (GO) was found to catalyze the reduction of carbon tetrachloride by layered Fe(II)-Fe(III) hydroxide (Green R....... This study indicates that traces of graphene oxide can affect reaction pathways as well as kinetics for dechlorination processes in anoxic sediments by facilitating a partial dechlorination....

  12. Four-Wire Impedance Spectroscopy on Planar Zeolite/Chromium Oxide Based Hydrocarbon Gas Sensors

    Directory of Open Access Journals (Sweden)

    Ralf Moos

    2007-11-01

    Full Text Available Impedometric zeolite hydrocarbon sensors with a chromium oxide intermediatelayer show a very promising behavior with respect to sensitivity and selectivity. Theunderlying physico-chemical mechanism is under investigation at the moment. In order toverify that the effect occurs at the electrode and that zeolite bulk properties remain almostunaffected by hydrocarbons, a special planar setup was designed, which is very close to realsensor devices. It allows for conducting four-wire impedance spectroscopy as well as two-wire impedance spectroscopy. Using this setup, it could be clearly demonstrated that thesensing effect can be ascribed to an electrode impedance. Furthermore, by combining two-and four-wire impedance measurements at only one single frequency, the interference of thevolume impedance can be suppressed and an easy signal evaluation is possible, withouttaking impedance data at different frequencies.

  13. CO2 as an Oxidant for High Temperature Reactions

    Directory of Open Access Journals (Sweden)

    Sibudjing eKawi

    2015-03-01

    Full Text Available This paper presents a review on the developments in catalyst technology for the reactions utilizing CO2 for high temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene and finally CO2 reforming of hydrocarbon feedstock (i.e. methane and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However some reactions, such as CO2 reforming of ethanol and glycerol which have not reached industrial scale are also reviewed owing to their great potential in terms of sustainability which are essential as energy for the future. This review further illustrates the building-up of knowledge which shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts which can be adapted for the multiple CO2-related reactions.

  14. A novel tandem Betti/Ullmann oxidation reaction as an efficient route ...

    Indian Academy of Sciences (India)

    Betti reaction; cross-coupling reaction; oxidation; heterogeneous catalysis. Abstract. A novel tandem Betti/Ullmann/oxidation reaction was used for synthesis of new oxazepine derivatives containing kojic acid. This protocol ... This method provides a new and useful strategy for the construction of heterocycles. Also novel Betti ...

  15. Hydrocarbons and air pollution

    International Nuclear Information System (INIS)

    Herz, O.

    1992-01-01

    This paper shows the influence of hydrocarbons vapors, emitted by transports or by volatile solvents using, on air pollution. Hydrocarbons are the principal precursors of photochemical pollution. After a brief introduction on atmospheric chemistry and photochemical reactions, the author describes the french prevention program against hydrocarbons emissions. In the last chapter, informations on international or european community programs for photochemical pollution study are given. 5 figs., 10 tabs

  16. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  17. High Pressure Preignition Chemistry of Hydrocarbons and Hydrocarbon Mixtures

    National Research Council Canada - National Science Library

    Cernansky, N.P

    1998-01-01

    .... The research program entailed mechanistic studies examining the oxidation chemistry of single-component hydrocarbons and ignition studies examining the overall ignition of pure single component fuels and fuel blends...

  18. Rate constants and temperature effects for reactions of Cl2sm-bullet- with unsaturated alcohols and hydrocarbons in aqueous and acetonitrile/water solutions

    International Nuclear Information System (INIS)

    Padmaja, S.; Neta, P.; Huie, R.E.

    1992-01-01

    Absolute rate constants for reactions of the dichlorine radical anion, Cl 2 sm-bullet- , with unsaturated alcohols and hydrocarbons have been measured at various temperatures. The alcohol reactions were measured in aqueous solutions and the hydrocarbon reactions in 1:1 aqueous acetonitirle (ACN) solutions. The rate constants for two alcohols and one hydrocarbon were also examined as a function of solvent composition. The room temperature rate constants varied between 10 6 and 10 9 M -1 s -1 . The pre-exponential factors, A, were about (1-5) x 10 9 M -1 s -1 for the alcohols in aqueous solutions and about (0.1-1) x 10 9 M -1 s -1 for the hydrocarbons in aqueous ACN solutions. The activation energies, E a , varied considerably, between 4 and 12 kJ mol -1 for the alcohols and between 2 and 8 kJ mol -1 for the hydrocarbons. The rate constants, k 298 , decrease with increasing ionization potential (IP) of the unsaturated compound, in agreement with an electrophilic addition mechanism. The activation energies for the unsaturated alcohols decrease when the IP decreases from 9.7 to 9.1 eV but appear to level off at lower IP. Most alkenes studied had IP a . Upon addition of ACN to the aqueous solution, the values of log k 298 decreased linearly by more than 1 order of magnitude with increasing ACN mole fraction. This decrease appears to result from a combination of changes in the activation energy and in the pre-exponential factor. The reason for these changes may lie in changes in the solvation shell of the Cl 2 sm-bullet- radical, which will affect the A factor, in combination with changes in solvation of Cl - , which will affect the energetics of the reactions as well. 20 refs., 7 figs., 6 tabs

  19. Oxidative coupling of methane. Still a challenge for catalyst development and reaction engineering

    Energy Technology Data Exchange (ETDEWEB)

    Schomaecker, R.; Arnd, S.; Beck, B. [Technical Univ. of Berlin (Germany). Dept. of Chemistry] [and others

    2013-11-01

    The oxidative coupling of methane to ethylene offers great industrial potential, because it would broaden the feedstock basis for chemical industry. Because methane is the most stable hydrocarbon, its activation requires high temperatures and it is a great scientific challenge to overcome the apparent yield limit of about 25%. This barrier has never been exceeded since the beginning of OCM research more than 20 years ago. Results and Discussion: This challenge is one of the key projects of the Cluster of Excellence UNICAT and requires joined efforts and contributions from many disciplines, because this reaction shows a combined surface/gas phase reaction mechanism which results in very unusual and complex dependencies on the reaction conditions. Although dozens of materials are known to catalyze the reaction, the selection of a catalyst suitable for an industrial process is difficult, due to severe stability problems of many materials. Li/MgO was chosen by the UNICAT-team as model catalyst, because of the extended literature about it. But it shows uncontrollable deactivation, no matter what precursor and method were used for its preparation. Nevertheless, it is a suitable catalyst for fundamental studies, due to its formal chemical simplicity. A key result of the joined research activities was the disproval of the Lunsford mechanism and the elucidation of the real function of lithium as a surface modifier creating a rough and defect-rich surface. For the development of an OCM process another catalyst, Na{sub 2}WO{sub 4}/Mn/SiO{sub 2}, was chosen from the rich literature on OCM. Although less is known about its structure and the reaction mechanism at this catalyst, its stability was the most important reason to select it for further engineering studies. Kinetic isotope measurements and studies in a TAP reactor demonstrate the similarity of the reaction mechanisms at both catalysts, despite the completely different materials. The selectivity is largely controlled by

  20. MULTICOMPONENT DETERMINATION OF CHLORINATED HYDROCARBONS USING A REACTION-BASED CHEMICAL SENSOR .2. CHEMICAL SPECIATION USING MULTIVARIATE CURVE RESOLUTION

    NARCIS (Netherlands)

    Tauler, R.; Smilde, A. K.; HENSHAW, J. M.; BURGESS, L. W.; KOWALSKI, B. R.

    1994-01-01

    A new multivariate curve resolution method that can extract analytical information from UV/visible spectroscopic data collected from a reaction-based chemical sensor is proposed. The method is demonstrated with the determination of mixtures of chlorinated hydrocarbons by estimating the kinetic and

  1. An investigation of molybdenum and molybdenum oxide catalyzed hydrocarbon formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tysoe, W.T.

    1995-09-01

    The document is divided into: experiments on model catalysts at high pressure, reaction studies on metallic Mo, surface chemistry experiments (metallic surfaces in ultrahigh vacuum; Mo(CO){sub 6} adsorption on alumina), and theoretical calculations.

  2. Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

    DEFF Research Database (Denmark)

    Thomsen, A.B.

    1998-01-01

    The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

  3. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  4. Effects of methyl group on aromatic hydrocarbons on the nanostructures and oxidative reactivity of combustion-generated soot

    KAUST Repository

    Guerrero Peñ a, Gerardo D.J.; Alrefaai, Mhd Maher; Yang, Seung Yeon; Raj, Abhijeet; Brito, Joaquin L.; Stephen, Samuel; Anjana, Tharalekshmy; Pillai, Vinu; Al Shoaibi, Ahmed; Chung, Suk-Ho

    2016-01-01

    The substituted and unsubstituted aromatic hydrocarbons, present in transportation fuels such as gasoline and diesel, are thought to be responsible for most of the soot particles produced during their combustion. However, the effects of the substituted alkyl groups on the aromatic hydrocarbons on their sooting tendencies, and on the physical and chemical properties of soot produced from them are not well understood. In this work, the effect of the presence of methyl groups on aromatic hydrocarbons on their sooting propensity, and on the oxidative reactivity, morphology, and chemical composition of soot generated from them in diffusion flames is studied using benzene, toluene, and m-xylene as fuels. Several experimental techniques including high resolution transmission electron microscopy and X-ray diffraction are used to identify the morphological changes in soot, whereas the elemental and thermo-gravimetric analyses, electron energy loss spectroscopy, and Fourier transform infrared spectroscopy are used to study the changes in its chemical properties and reactivity. The activation energies for soot oxidation are calculated at different conversion levels, and a trend in the reactivity of soots from benzene, toluene and m-xylene is reported. It is observed that the sizes of primary particles and graphene-like sheets, and the concentrations of aliphatics and oxygenated groups in soot particles decreased with the addition of methyl group(s) on the aromatic ring. The physicochemical changes in soot are found to support the oxidative reactivity trends. © 2016 The Combustion Institute

  5. Effects of methyl group on aromatic hydrocarbons on the nanostructures and oxidative reactivity of combustion-generated soot

    KAUST Repository

    Guerrero Peña, Gerardo D.J.

    2016-07-23

    The substituted and unsubstituted aromatic hydrocarbons, present in transportation fuels such as gasoline and diesel, are thought to be responsible for most of the soot particles produced during their combustion. However, the effects of the substituted alkyl groups on the aromatic hydrocarbons on their sooting tendencies, and on the physical and chemical properties of soot produced from them are not well understood. In this work, the effect of the presence of methyl groups on aromatic hydrocarbons on their sooting propensity, and on the oxidative reactivity, morphology, and chemical composition of soot generated from them in diffusion flames is studied using benzene, toluene, and m-xylene as fuels. Several experimental techniques including high resolution transmission electron microscopy and X-ray diffraction are used to identify the morphological changes in soot, whereas the elemental and thermo-gravimetric analyses, electron energy loss spectroscopy, and Fourier transform infrared spectroscopy are used to study the changes in its chemical properties and reactivity. The activation energies for soot oxidation are calculated at different conversion levels, and a trend in the reactivity of soots from benzene, toluene and m-xylene is reported. It is observed that the sizes of primary particles and graphene-like sheets, and the concentrations of aliphatics and oxygenated groups in soot particles decreased with the addition of methyl group(s) on the aromatic ring. The physicochemical changes in soot are found to support the oxidative reactivity trends. © 2016 The Combustion Institute

  6. Solid-phase vibrational redox reactions in coordinated oxides

    International Nuclear Information System (INIS)

    Kostikova, G.P.; Korol'kov, D.V.; Kostikov, Yu.P.

    1996-01-01

    The properties of multicomponent oxides (YBa 2 Cu 3 O 7-x , etc.), incorporating different valency forms of each of two (or more) different elements have been compared with the properties of the known chemical systems, where vibrational (periodic) redox-reactions are realized a fortiori. The essence of the new theoretical concept suggested consists in the following: high-T c superconductivity of the complex oxides and similar compounds originates from vibrational redox reaction proceeding in solid phase and involving different valency atoms of every element

  7. Reactions of organic zinc- and cadmium elementoxides with ethylene oxide

    International Nuclear Information System (INIS)

    Dodonov, V.A.; Krasnov, Yu.N.

    1980-01-01

    Studied are reactions of triphenylmethoxy, -triphenylsiloxyethylzinc and -cadmium with ethylene oxide in ratio of 1:1. Reactions have been carried out in tolyene solutions in ampules sealed in argon atmosphere. It is found that interaction of triphenylsiloxy-, triphenylmethoxyethylcadmium and triphenylsiloxyethylzinc with ethylene oxide occurs at the metal-carbon bond with formation of implantation products. Triphenylmethoxyethylzinc reacts with ethylene oxide both at the metal-carbon and metal-oxygen bonds. Alkoxytriphenylsiloxyderivatives of zinc and cadmium are thermally instable and decompose under the conditions of reaction (130 deg C) with migration of phenyl group from silicon to zinc or cadmium, giving alkoxyphenylderivative and with bensene splitting out

  8. Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

    Directory of Open Access Journals (Sweden)

    Gerardo Carlos Torres

    2012-01-01

    Full Text Available A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

  9. Liquid hydrocarbons from coal beds – risk factor for the underground work environment - Case study

    Directory of Open Access Journals (Sweden)

    Tomescu Cristian

    2017-01-01

    Full Text Available Liquid hydrocarbons from the coal bed and surrounding rocks, besides the stored gases, methane, carbon dioxide, carbon oxide, generate the increase of the risk factor from the occupational health and safety point of view. If for reducing the gas concentrations level and the methane emissions in order to increase the safety in exploitation exist well-known solutions and methods, the oxidation or self-oxidation of the hydrocarbons from the coal bed generate a series of compounds, reaction products over maximum admitted concentrations which give birth to a toxic atmosphere and which is hazardous for workers, at the same time inducing an error in noting the occurrence of a spontaneous combustion phenomena, a major risk for the workers and for the mineral resource. This paper represents a case study performed in one underground mine unit from Jiu Valley and presents the analysis for underground environment factors monitoring and for solutions for diminishing the OHS risk factors.

  10. Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for In Situ Combustion Process

    Directory of Open Access Journals (Sweden)

    Alexandra Ushakova

    2017-01-01

    Full Text Available Despite the abundance of in situ combustion models of oil oxidation, many of the effects are still beyond consideration. For example, until now, initial stages of oxidation were not considered from a position of radical chain process. This is a serious difficulty for the simulation of oil recovery process that involves air injection. To investigate the initial stages of oxidation, the paper considers the sequence of chemical reactions, including intermediate short-living compounds and radicals. We have attempted to correlate the main stages of the reaction with areas of heat release observed in the experiments. The system of differential equations based on the equations of oxidation reactions was solved. Time dependence of peroxides formation and start of heat release is analytically derived for the initial stages. We have considered the inhibition of initial oxidation stages by aromatic oil compounds and have studied the induction time in dependence on temperature. Chain ignition criteria for paraffins and crude oil in presence of core samples were obtained. The calculation results are compared with the stages of oxidation that arise by high-pressure differential scanning calorimetry. According to experimental observations we have determined which reactions are important for the process and which can be omitted or combined into one as insignificant.

  11. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    Science.gov (United States)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  12. The photochemical reaction of hydrocarbons under extreme thermobaric conditions

    Science.gov (United States)

    Serovaiskii, Aleksandr; Kolesnikov, Anton; Mukhina, Elena; Kutcherov, Vladimir

    2017-10-01

    The photochemical reaction of hydrocarbons was found to play an important role in the experiments with the synthetic petroleum conducted in Diamond Anvil Cell (DAC). Raman spectroscopy with a green laser (514.5 nm) was used for in situ sample analysis. This photochemical effect was investigated in the pressure range of 0.7-5 GPa, in the temperature interval from the ambient conditions to 450°C. The power of laser used in these experiment series was from 0.05 W to 0.6 W. The chemical transformation was observed when the necessary threshold pressure (~2.8 GPa) was reached. This transformation correlated with the luminescence appearance on the Raman spectra and a black opaque spot in the sample was observed in the place where the laser focus was forwarded. The exposure time and laser power (at least in the 0.1-0.5 W range) did not play a role in the 0.1-0.5 GPa range.

  13. Purifying hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Demoulins, H D; Garner, F H

    1923-02-07

    Hydrocarbon distillates, including natural gases and vapors produced by cracking hydrocarbon oils, are desulfurized etc. by treating the vapor with an aqueous alkaline solution of an oxidizing agent. The hydrocarbons may be previously purified by sulfuric acid. In examples aqueous solutions of sodium or calcium hydrochlorite containing 1.5 to 5.0 grams per liter of available chlorine and sufficient alkali to give an excess of 0.1 percent in the spent reagent are preheated to the temperature of the vapor, and either sprayed or atomized into the vapors near the outlet of the dephlegmator or fractionating tower, or passed in countercurrent to the vapors through one or a series of scrubbers.

  14. Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

    Science.gov (United States)

    Sundararaman, Ramanathan

    Conventional approaches to oxidative desulfurization of liquid hydrocarbons involve use of high-purity, expensive water soluble peroxide for oxidation of sulfur compounds followed by post-treatment for removal of oxidized sulfones by extraction. Both are associated with higher cost due to handling, storage of oxidants and yield loss with extraction and water separation, making the whole process more expensive. This thesis explores an oxidative desulfurization process using air as an oxidant followed by catalytic decomposition of sulfones thereby eliminating the aforementioned issues. Oxidation of sulfur compounds was realized by a two step process in which peroxides were first generated in-situ by catalytic air oxidation, followed by catalytic oxidation of S compounds using the peroxides generated in-situ completing the two step approach. By this technique it was feasible to oxidize over 90% of sulfur compounds present in real jet (520 ppmw S) and diesel (41 ppmw S) fuels. Screening of bulk and supported CuO based catalysts for peroxide generation using model aromatic compound representing diesel fuel showed that bulk CuO catalyst was more effective in producing peroxides with high yield and selectivity. Testing of three real diesel fuels obtained from different sources for air oxidation over bulk CuO catalyst showed different level of effectiveness for generating peroxides in-situ which was consistent with air oxidation of representative model aromatic compounds. Peroxides generated in-situ was then used as an oxidant to oxidize sulfur compounds present in the fuel over MoO3/SiO2 catalyst. 81% selectivity of peroxides for oxidation of sulfur compounds was observed on MoO3/SiO2 catalyst at 40 °C and under similar conditions MoO3/Al2O3 gave only 41% selectivity. This difference in selectivity might be related to the difference in the nature of active sites of MoO3 on SiO2 and Al2O 3 supports as suggested by H2-TPR and XRD analyses. Testing of supported and bulk Mg

  15. Effect of Ce2O3, La2O3 and ZnO additives on the oxygenates conversion into liquid hydrocarbons

    Science.gov (United States)

    Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

    2018-01-01

    A selective modifying effect of cerium, magnesium and zinc oxide additives on the activity and the selectivity of a pentasil group zeolite catalyst in the reaction of conversion of oxygenates (methanol and dimethyl ether) to liquid hydrocarbons was found. It was found that zinc oxide contributes to the stable operation of the zeolite catalyst in the conversion of oxygenates in the synthesis gas stream and leads to the production of gasolines with low durene content (not more than 6.1 wt%). The obtained results demonstrate the rationale for producing hydrocarbons from synthesis gas without the stage of oxygenate separation with their subsequent conversion to synthetic gasoline.

  16. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

  17. Technologies for hydrogen production based on direct contact of gaseous hydrocarbons and evaporated water with Molten Pb or Pb-Bi

    International Nuclear Information System (INIS)

    Gulevich, A. V.; Martynov, P. N.; Gulevsky, V. A.; Ulyanov, V. V.

    2007-01-01

    hydrogen (at t≥500 degree C). A valuable product is formed in this process - powdery carbon readily removable from the reaction zone owing to a large density difference of carbon vs. liquid metal. 3. The oxidation conversion of hydrocarbons (at t≥500 degree C). Hydrogen and CO 2 , hydrogen and synthetic gas (H 2 and CO mixture) can be obtained as end products. This process develops more effectively compared to the traditional vapor conversion. The increase of conversion effectiveness is caused by the new processes not employed before: hydrocarbon oxidation by oxides present in the reaction zone as dissolved in the melt and in solid phase; co-oxidation of hydrocarbons by evaporated water and HLMC oxides. As a result of enhanced effectiveness of oxidation conversion, the conditions for its fulfillment can be considerably simplified - the working pressure, as well as the process temperature can be decreased to the level at which it becomes possible to use structural materials, equipment, and appropriate measures for the employment of technology with coolants that have been developed and substantiated for operation in circuits with Pb and Pb-Bi coolants. The dimensions of 'direct contact' devices for hydrogen production can be very small. Therefore, they can find application both in large-scale hydrogen production, and in small-size (remote) sources of hydrogen

  18. Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

    Science.gov (United States)

    Kashiwagi, Takashi; Nambu, Hidesaburo

    1992-01-01

    Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

  19. Steam hydrocarbon cracking and reforming

    NARCIS (Netherlands)

    Golombok, M.

    2004-01-01

    Many industrial chemical processes are taught as distinct contrasting reactions when in fact the unifying comparisons are greater than the contrasts. We examine steam hydrocarbon reforming and steam hydrocarbon cracking as an example of two processes that operate under different chemical reactivity

  20. Process for manufacture of a catalyst suitable for the steam reforming of hydrocarbons and for obtaining methane

    Energy Technology Data Exchange (ETDEWEB)

    Golebiowski, A.; Romotowski, T.; Hennel, W.; Wroblewska-Wroblewska, T.; Polanski, A.; Janecki, Z.; Paluch-Paluch, S.

    1982-07-29

    The invention concerns a process for the manufacture of a catalyst suitable for the steam reforming of hydrocarbons or for obtaining methane, by the deposition of the catalytic components on a metal carrier with a large surface area, particularly a process for the manufacture of a solid nickel catalyst, which is suitable for the steam reforming of hydrocarbons, particularly of methane. The following steps of the process are carried out: producing a highly porous layer of spongy metal from Ni powder on the side of a metal wall away from a heat medium, which separates the reaction mixture from the heat medium, then separate application of a non-reducing oxide (Al/sub 2/O/sub 3/) and a reducing oxide (nickel oxide) on the spongy metal by soaking with metal salt solution and then roasting in the temperature range of 400 to 1200/sup 0/C.

  1. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Powell, J; Kaplan, A F H [Department of Applied Physics and Mechanical Engineering, Luleaa University of Technology, SE-971 87 Luleaa (Sweden); Petring, D [Fraunhofer-Institute for Laser Technology (ILT), Steinbachstrasse 15, Aachen (Germany); Kumar, R V [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ (United Kingdom); Al-Mashikhi, S O; Voisey, K T [Department of Mechanical, Materials and Manufacturing Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)], E-mail: jpowell@laserexp.co.uk

    2009-01-07

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  2. Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

    International Nuclear Information System (INIS)

    Powell, J; Kaplan, A F H; Petring, D; Kumar, R V; Al-Mashikhi, S O; Voisey, K T

    2009-01-01

    In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

  3. Adsorption of polycyclic aromatic hydrocarbons on graphene oxides and reduced graphene oxides.

    Science.gov (United States)

    Sun, Yubing; Yang, Shubin; Zhao, Guixia; Wang, Qi; Wang, Xiangke

    2013-11-01

    Graphene has attracted increasing attention in multidisciplinary studies because of its unique physical and chemical properties. Herein, the adsorption of polycyclic aromatic hydrocarbons (PAHs), such as naphthalene (NAP), anthracene (ANT), and pyrene (PYR), on reduced graphene oxides (rGOs) and graphene oxides (GOs) as a function of pH, humic acid (HA), and temperature were elucidated by means of a batch technique. For comparison, nonpolar and nonporous graphite were also employed in this study. The increasing of pH from 2 to 11 did not influence the adsorption of PAHs on rGOs, whereas the suppressed adsorption of NAP on rGOs was observed both in the presence of HA and under high-temperature conditions. Adsorption isotherms of PAHs on rGOs were in accordance with the Polanyi-Dubinin-Ashtahhov (PDA) model, providing evidence that pore filling and flat surface adsorption were involved. The saturated adsorbed capacities (in mmol g(-1)) of rGOs for PAHs calculated from the PDA model significantly decreased in the order of NAP>PYR>ANT, which was comparable to the results of theoretical calculations. The pore-filling mechanism dominates the adsorption of NAP on rGOs, but the adsorption mechanisms of ANT and PYR on rGOs are flat surface adsorption. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Relationship between measurements of blood oxidative metabolites and skin reaction in irradiated rats

    International Nuclear Information System (INIS)

    Kaneko, Takashi; Goto, Jun; Nomiya, Takuma; Nemoto, Kenji

    2011-01-01

    Recently, oxidative metabolites have been able to be measured by simple small device. It has been reported that the value of oxidative metabolites increases under several conditions such as hypertension, smoking, diabetes mellitus, etc. Radiation used in radiotherapy also causes free radicals and oxidative metabolites, and irradiation causes dermatitis and sometimes causes skin ulcer in the irradiated site. We analyzed the relationships between the value of oxidative metabolites and skin reactions. A certain doses of radiation were irradiated to the right thigh of rats, and oxidative metabolites of rat's blood from caudal vein were measured by d-reactive oxygen metabolites (ROMs) test using an exclusive device. Skin reactions were evaluated according to a skin-reaction grading system from the day before irradiation to day 38 after irradiation. As a results, a significant correlation was shown between irradiation dose and skin grade. And a significant correlation was also shown between the value of oxidative metabolites and irradiation dose. The increase in oxidative metabolites was seen in the Day 16 after irradiation, and that corresponded with the appearance of skin reaction. It was suggested that the value of oxidative metabolites seems to be useful for estimating degree of skin reaction and time to appear skin reaction after irradiation. (author)

  5. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  6. Metalloporphyrins immobilized in Fe3O4@SiO2 mesoporous submicrospheres: Reusable biomimetic catalysts for hydrocarbon oxidation.

    Science.gov (United States)

    Barbosa, Isaltino A; de Sousa Filho, Paulo C; da Silva, Douglas L; Zanardi, Fabrício B; Zanatta, Lucas D; de Oliveira, Adilson J A; Serra, Osvaldo A; Iamamoto, Yassuko

    2016-05-01

    We successfully immobilized metalloporphyrins (MeP) in mesoporous silica coating magnetite spheres. In this sense, we prepared two different classes of core@shell supports, which comprise aligned (Fe3O4-AM-MeP, MeP=FeP or MnP) and non-aligned (Fe3O4-NM-MeP, MeP=FeP or MnP) mesoporous magnetic structures. X-ray diffractometry and energy dispersive X-ray spectroscopy confirmed the mesoporous nature of the silica shell of the materials. Magnetization measurements, scanning and transmission electron microscopies (SEM/TEM), electrophoretic mobility (ζ-potential), and infrared spectroscopy (FTIR) also confirm the composition and structure of the materials. The catalysts maintained their catalytic activity during nine reaction cycles toward hydrocarbon oxidation processes without detectable catalyst leaching. The catalysis results revealed a biomimetic pattern of cytochrome P450-type enzymes, thus confirming that the prepared materials are can effectively mimic the activity of such groups. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. CO{sub 2} as an Oxidant for High-Temperature Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kawi, Sibudjing, E-mail: chekawis@nus.edu.sg; Kathiraser, Yasotha [Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, Singapore (Singapore)

    2015-03-18

    This paper presents a review on the developments in catalyst technology for the reactions utilizing CO{sub 2} for high-temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene, and finally CO{sub 2} reforming of hydrocarbon feedstock (i.e., methane) and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However, some reactions, such as CO{sub 2} reforming of ethanol and glycerol, which have not reached industrial scale, are also reviewed owing to their great potential in terms of sustainability, which is essential as energy for the future. This review further illustrates the building-up of knowledge that shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts, which can be adapted for the multiple CO{sub 2}-related reactions.

  8. Production of light hydrocarbons, etc. [from heavy hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    1937-10-07

    A process is given for the production of light hydrocarbons of the gasoline type and, if desired, of the middle-oil type, from liquid or fusible heavy or medium heavy hydrocarbon materials. The process comprises subjecting the said initial materials in the first stage to catalytic hydrofining, separating the lower boiling constituents and the hydrogenating gas from the resulting products and then subjecting the higher boiling constituents in a second stage to a splitting destructive hydrogenation and then recycling substantially the entire reaction mixture obtained in the second stage to the frst stage.

  9. Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

    Science.gov (United States)

    Hunkeler, Daniel; Höhener, Patrick; Bernasconi, Stefano; Zeyer, Josef

    1999-04-01

    A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH 4, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O 2 and NO 3-) were consumed, elevated concentrations of Fe(II), Mn(II), CH 4, alkalinity and DIC were detected and the DIC was generally depleted in 13C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.

  10. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  11. Identification of Novel Methane-, Ethane-, and Propane-Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing ▿ †

    Science.gov (United States)

    Redmond, Molly C.; Valentine, David L.; Sessions, Alex L.

    2010-01-01

    Marine hydrocarbon seeps supply oil and gas to microorganisms in sediments and overlying water. We used stable isotope probing (SIP) to identify aerobic bacteria oxidizing gaseous hydrocarbons in surface sediment from the Coal Oil Point seep field located offshore of Santa Barbara, California. After incubating sediment with 13C-labeled methane, ethane, or propane, we confirmed the incorporation of 13C into fatty acids and DNA. Terminal restriction fragment length polymorphism (T-RFLP) analysis and sequencing of the 16S rRNA and particulate methane monooxygenase (pmoA) genes in 13C-DNA revealed groups of microbes not previously thought to contribute to methane, ethane, or propane oxidation. First, 13C methane was primarily assimilated by Gammaproteobacteria species from the family Methylococcaceae, Gammaproteobacteria related to Methylophaga, and Betaproteobacteria from the family Methylophilaceae. Species of the latter two genera have not been previously shown to oxidize methane and may have been cross-feeding on methanol, but species of both genera were heavily labeled after just 3 days. pmoA sequences were affiliated with species of Methylococcaceae, but most were not closely related to cultured methanotrophs. Second, 13C ethane was consumed by members of a novel group of Methylococcaceae. Growth with ethane as the major carbon source has not previously been observed in members of the Methylococcaceae; a highly divergent pmoA-like gene detected in the 13C-labeled DNA may encode an ethane monooxygenase. Third, 13C propane was consumed by members of a group of unclassified Gammaproteobacteria species not previously linked to propane oxidation. This study identifies several bacterial lineages as participants in the oxidation of gaseous hydrocarbons in marine seeps and supports the idea of an alternate function for some pmoA-like genes. PMID:20675448

  12. Self-ignition and oxidation of various hydrocarbons between 600 and 1000 K at high pressure: experimental study with fast compression machine and modeling; Autoinflammation et oxydation de divers hydrocarbures entre 600 et 1000 K a haute pression: etude experimentale en machine a compression rapide et modelisation

    Energy Technology Data Exchange (ETDEWEB)

    Ribaucour, M.

    2002-12-01

    Low- and intermediate-temperature oxidation and self-ignition of hydrocarbons play a major role in spark ignition, diesel and HCCI (homogenous charge compression ignition) engines. A deep understanding of the chemistry linked with both phenomena is necessary to improve the engines efficiency and to reduce the formation of pollutants. This document treats of works about the self-ignition and oxidation at high pressure of various hydrocarbons between 600 and 1000 deg. K. The experimental tool used is a fast compression machine fitted with a fast sampling system for the measurement of self-ignition delays and of the concentrations of intermediate oxidation products. The advantages and limitations of this tool are discussed. The self-ignition of various hydrocarbons is compared using pre-defined data which characterize the phenomenologies like cold flames, negative temperature coefficients and self-ignition limits. The hydrocarbons considered are pure or binary mixtures of alkanes, pent-1-ene and n-butyl-benzene. The development of high pressure oxidation reaction schemes of alkanes between 600 and 1000 deg. K is described. It is directly based on the analysis of intermediate oxidation products. This methodology is also applied to pent-1-ene and n-butyl-benzene. The construction of detailed thermo-kinetic models of oxidation and the modeling of phenomena are made for n-butane, n-heptane, for the 3 pentane isomers, for pent-1-ene and n-butyl-benzene. Finally, the perspectives of future works are evoked. They concern new modeling and new methodologies to be applied in more predictive thermo-kinetic models and the reduction of detailed models in order to include them inside fluid dynamics codes. (J.S.)

  13. Remediation of total petroleum hydrocarbons using combined in-vessel composting ‎and oxidation by activated persulfate

    Directory of Open Access Journals (Sweden)

    A.R. Asgari

    2017-12-01

    Full Text Available This study was investigated the efficiency of activated persulfate and ‎in-vessel composting for removal of total petroleum hydrocarbons. ‎Remediation by activated persulfate with ferrous sulfate as pre-treatment was done at batch system. In the chemical oxidation, various variables including persulfate concentrations (10-3000 mg/g as waste, pH (3-7, ferrous sulfate (0.5-4 mg/g as wasteand temperature (20-60°C were studied. In the biological system, premature compost was added as an amendment. The filter cake to compost ratio were 1:0 (as control and 1:5 to 15 (as dry basis. C: N: P ratio and moisture content were 100:5:1 and 45-60%, respectively. The results showed that acidic pH (pH=3 had high efficiency for the removal of total petroleum hydrocarbons by activated persulfate. Temperature had the significant effect during the persulfate oxidation. When ferrous sulfate was used as an activator for degradation at acidic condition and 60°C, removal efficiency increased to 47.32%. The results of biological process showed that the minimum total petroleum hydrocarbons removal in all reactors was 62 percent. The maximum and minimum removal efficiency was obtained at 1:5 (69.46% and 1:10 (62.42% mixing ratios, respectively. Kinetic study showed that second order kinetic model (R2>0.81 shows the best agreement with the experimental data and the rate of TPH degradation at low mixing ratio (1:3 was faster than high mixing ratio (1:15. Therefore, according to the results, in-vessel composting after pre-treatment by activated persulfate is suggested as an efficient process for degradation of total petroleum hydrocarbons.

  14. Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

    International Nuclear Information System (INIS)

    Rocek, J.; Peng, T.Y.

    1977-01-01

    Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

  15. Process for conversion of lignin to reformulated hydrocarbon gasoline

    Science.gov (United States)

    Shabtai, Joseph S.; Zmierczak, Wlodzimierz W.; Chornet, Esteban

    1999-09-28

    A process for converting lignin into high-quality reformulated hydrocarbon gasoline compositions in high yields is disclosed. The process is a two-stage, catalytic reaction process that produces a reformulated hydrocarbon gasoline product with a controlled amount of aromatics. In the first stage, a lignin material is subjected to a base-catalyzed depolymerization reaction in the presence of a supercritical alcohol as a reaction medium, to thereby produce a depolymerized lignin product. In the second stage, the depolymerized lignin product is subjected to a sequential two-step hydroprocessing reaction to produce a reformulated hydrocarbon gasoline product. In the first hydroprocessing step, the depolymerized lignin is contacted with a hydrodeoxygenation catalyst to produce a hydrodeoxygenated intermediate product. In the second hydroprocessing step, the hydrodeoxygenated intermediate product is contacted with a hydrocracking/ring hydrogenation catalyst to produce the reformulated hydrocarbon gasoline product which includes various desirable naphthenic and paraffinic compounds.

  16. Purifying hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    Rostin, H

    1938-08-11

    A process is described for continuously purifying hydrocarbon oils consisting in conducting the vapors of the same at a temperature of 300 to 400/sup 0/C over the oelitic ore minette together with reducing gases in presence of steam the proportion of the reducing gases and steam being such that the sulfur of the hydrocarbons escapes from the reaction chamber in the form of sulfuretted hydrogen without permanent sulfide of iron being formed.

  17. Raman and photoelectron spectroscopic investigation of high-purity niobium materials: Oxides, hydrides, and hydrocarbons

    Science.gov (United States)

    Singh, Nageshwar; Deo, M. N.; Nand, Mangla; Jha, S. N.; Roy, S. B.

    2016-09-01

    We present investigations of the presence of oxides, hydrides, and hydrocarbons in high-purity (residual resistivity ratio, ˜300) niobium (Nb) materials used in fabrication of superconducting radio frequency (SRF) cavities for particle accelerators. Raman spectroscopy of Nb materials (as-received from the vendor as well as after surface chemical- and thermal processing) revealed numerous peaks, which evidently show the presence of oxides (550 cm-1), hydrides (1277 and 1385 cm-1: ˜80 K temperature), and groups of hydrocarbons (1096, 2330, 2710, 2830, 2868, and 3080 cm-1). The present work provides direct spectroscopic evidence of hydrides in the electropolished Nb materials typically used in SRF cavities. Raman spectroscopy thus can provide vital information about the near-surface chemical species in niobium materials and will help in identifying the cause for the performance degradation of SRF cavities. Furthermore, photoelectron spectroscopy was performed on the Nb samples to complement the Raman spectroscopy study. This study reveals the presence of C and O in the Nb samples. Core level spectra of Nb (doublet 3d5/2 and 3d3/2) show peaks near 206.6 and 209.4 eV, which can be attributed to the Nb5+ oxidation state. The core level spectra of C 1 s of the samples are dominated by graphitic carbon (binding energy, 284.6 eV), while the spectra of O 1 s are asymmetrically peaked near binding energy of ˜529 eV, and that indicates the presence of metal-oxide Nb2O5. The valence-band spectra of the Nb samples are dominated by a broad peak similar to O 2p states, but after sputtering (for 10 min) a peak appears at ˜1 eV, which is a feature of the elemental Nb atom.

  18. Evaluation of the Removal of Hydrocarbons from Soil Media Using Persulfate Oxidation in the Presence of Mineral Siderite

    Directory of Open Access Journals (Sweden)

    Farzad Mohammadi

    2016-09-01

    Full Text Available Introduction and purpose: Soil contamination by petroleum is mostly resulted from oil exploration, refining processes, leaking of oil products from storage tanks, leaking from pipelines due to pipe friction and decay, refinery wastewater discharge and agricultural irrigation with such materials. Sodium persulfate (Na2S2O8, which is a chemical oxidant, could be activated in the presence of ferrous (Fe2+ and, leading to the treatment of a wide range of soil contaminants. Therefore, this study aimed to evaluate the removal of hydrocarbons from soil media using persulfate oxidation in the presence of mineral siderite. Methods: Initially, oil-contaminated soil was prepared in the form of two separate samples, including silt-clay and sandy-loam soils, which were orderly spiked with 5000 mg fuel oil per kilogram of dry soil. Following that, the effects of various factors, such as different concentrations of persulfate (100-500 mmol/L and siderite (0.1-0.5 g/L, pH (3-9 and temperature (20-60◦C and the removal of petroleum hydrocarbon were assessed.Results: In this study, the optimum condition for degeneration of total petroleum hydrocarbon in silt-clay soils was reported, as follows: temperature: 60◦C, pH: 3, and persulfate/siderite molar ratio of 400 mmol/L to 4.0 g/L. Meanwhile, the optimum condition for the removal of hydrocarbon from sandy-loam soils was pH: 3, temperature: 60◦C and persulfate/siderite molar ratio of 300 mmol/L to 3.0 g/L.Conclusion: According to the results of this study, the optimal amount of persulfate and siderite could be used to remove hydrocarbons from contaminated soils.

  19. In Situ Hydrocarbon Degradation by Indigenous Nearshore Bacterial Populations

    International Nuclear Information System (INIS)

    Cherrier, J.

    2005-01-01

    Potential episodic hydrocarbon inputs associated with oil mining and transportation together with chronic introduction of hydrocarbons via urban runoff into the relatively pristine coastal Florida waters poses a significant threat to Florida's fragile marine environment. It is therefore important to understand the extent to which indigenous bacterial populations are able to degrade hydrocarbon compounds and also determine factors that could potentially control and promote the rate at which these compounds are broken down in situ. Previous controlled laboratory experiments carried out by our research group demonstrated that separately both photo-oxidation and cometabolism stimulate bacterial hydrocarbon degradation by natural bacterial assemblages collected from a chronically petroleum contaminated site in Bayboro Bay, Florida. Additionally, we also demonstrated that stable carbon and radiocarbon abundances of respired CO 2 could be used to trace in situ hydrocarbon degradation by indigenous bacterial populations at this same site. This current proposal had two main objectives: (a) to evaluate the cumulative impact of cometabolism and photo-oxidation on hydrocarbon degradation by natural bacterial assemblages collected the same site in Bayboro Bay, Florida and (b) to determine if in situ hydrocarbon degradation by indigenous bacterial populations this site could be traced using natural radiocarbon and stable carbon abundances of assimilated bacterial carbon. Funds were used for 2 years of full support for one ESI Ph.D. student, April Croxton. To address our first objective a series of closed system bacterial incubations were carried out using photo-oxidized petroleum and pinfish (i.e. cometabolite). Bacterial production of CO 2 was used as the indicator of hydrocarbon degradation and (delta) 13 C analysis of the resultant CO 2 was used to evaluate the source of the respired CO 2 (i.e. petroleum hydrocarbons or the pinfish cometabolite). Results from these time

  20. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  1. Two-stage Catalytic Reduction of NOx with Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Umit S. Ozkan; Erik M. Holmgreen; Matthew M. Yung; Jonathan Halter; Joel Hiltner

    2005-12-21

    A two-stage system for the catalytic reduction of NO from lean-burn natural gas reciprocating engine exhaust is investigated. Each of the two stages uses a distinct catalyst. The first stage is oxidation of NO to NO{sub 2} and the second stage is reduction of NO{sub 2} to N{sub 2} with a hydrocarbon. The central idea is that since NO{sub 2} is a more easily reduced species than NO, it should be better able to compete with oxygen for the combustion reaction of hydrocarbon, which is a challenge in lean conditions. Early work focused on demonstrating that the N{sub 2} yield obtained when NO{sub 2} was reduced was greater than when NO was reduced. NO{sub 2} reduction catalysts were designed and silver supported on alumina (Ag/Al{sub 2}O{sub 3}) was found to be quite active, able to achieve 95% N{sub 2} yield in 10% O{sub 2} using propane as the reducing agent. The design of a catalyst for NO oxidation was also investigated, and a Co/TiO{sub 2} catalyst prepared by sol-gel was shown to have high activity for the reaction, able to reach equilibrium conversion of 80% at 300 C at GHSV of 50,000h{sup -1}. After it was shown that NO{sub 2} could be more easily reduced to N{sub 2} than NO, the focus shifted on developing a catalyst that could use methane as the reducing agent. The Ag/Al{sub 2}O{sub 3} catalyst was tested and found to be inactive for NOx reduction with methane. Through iterative catalyst design, a palladium-based catalyst on a sulfated-zirconia support (Pd/SZ) was synthesized and shown to be able to selectively reduce NO{sub 2} in lean conditions using methane. Development of catalysts for the oxidation reaction also continued and higher activity, as well as stability in 10% water, was observed on a Co/ZrO{sub 2} catalyst, which reached equilibrium conversion of 94% at 250 C at the same GHSV. The Co/ZrO{sub 2} catalyst was also found to be extremely active for oxidation of CO, ethane, and propane, which could potential eliminate the need for any separate

  2. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  3. Internal Displacement Reactions in Multicomponent Oxides: Part I. Line Compounds with Narrow Homogeneity Range

    OpenAIRE

    Reddy, SNS; Leonard, DN; Wiggins, LB; Jacob, KT

    2005-01-01

    As a model of an internal displacement reaction involving a ternary oxide line compound, the following reaction was studied at 1273 K as a function of time, t: $Fe+NiTiO_3 = Ni + FeTiO_3$ Both polycrystalline and single-crystal materials were used as the starting $NiTiO_3$ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a \\gamma -(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a consta...

  4. Multi-metallic oxides as catalysts for light alcohols and hydrocarbons from synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Perez, Miguel [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico); Diaz, L; Galindo, H de J; Dominguez, J. M; Salmon, Manuel [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)

    1999-08-01

    A series of Cu-Co-Cr oxides doped with alkaline metals (M), were prepared by the coprecipitation method with metal nitrates (Cu{sup I}I, CO{sup I}I, CR{sup I}II) and (M{sub 2})CO{sub 3} in aqueous solution. The calcined products were used as catalysts for the Fisher-Tropsch synthesis in a stainless-steel fixed bed microreactor. The material was characterized by x-ray diffraction, and the specific surface area, pore size and nitrogen adsorption-desorption properties were also determined. The alkaline metals favored the methanol synthesis and prevent the dehydration reactions whereas the hydrocarbon formation is independent to these metals. [Spanish] Una serie de oxidos Cu-Co-Cr soportados con metales alcalinos (M), fueron preparados por el metodo con nitratos metalicos (Cu{sup I}I, CO{sup I}I, CR{sup I}II) y (M{sub 2})CO{sub 3} en soluciones acuosas. Los productos calcinados fueron usados como catalizadores para la sintesis de Fisher-tropsch en la superficie fija de un microreactor de acero inoxidable. El material fue caracterizado por difraccion de rayos X y el area de superficie especifica, el tamano de poro y propiedades de absorcion-desorcion de nitrogeno fueron determinadas. Los metales alcalinos favorecieron la sintesis de metanol y previnieron las reacciones de deshidratacion, mientras que la formacion de hidrocarburos es independiente de estos metales.

  5. Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Patel, B.M.; Price, G.L.

    1990-01-01

    This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with 18 O 2 have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C 3 D 6 reaction. No isotope effect is observed for carbon dioxide formation from C 3 D 6 suggesting that CO 2 is formed by parallel, not consecutive, oxidation of propylene

  6. Studies On An Aerobic Oxidation Of Dibenzothiophene And Related Compounds Using Ruthenium Catalyst

    Directory of Open Access Journals (Sweden)

    Morishita Y.

    2015-06-01

    Full Text Available An aerobic oxidation of dibenzothiophene and related compounds using a catalytic amount of ruthenium chloride in hydrocarbon solvents at 80°C for 20 h gave the corresponding sulfones in almost quantitative yields. The reaction might proceed via autoxidation of solvents to hydroperoxides and the reaction of sulfur compounds with the resulting hydroperoxides.

  7. Hydrocarbon Plume Dynamics in the Worldś Most Spectacular Hydrocarbon Seeps, Santa Barbara Channel, California

    Science.gov (United States)

    Mau, S.; Reed, J.; Clark, J.; Valentine, D.

    2006-12-01

    Large quantities of natural gas are emitted from the seafloor into the coastal ocean near Coal Oil Point, Santa Barbara Channel (SBC), California. Methane, ethane, and propane were quantified in the surface water at 79 stations in a 270 km2 area in order to map the surficial hydrocarbon plume and to quantify air-sea exchange of these gases. A time series was initiated for 14 stations to identify the variability of the mapped plume, and biologically-mediated oxidation rates of methane were measured to quantify the loss of methane in surface water. The hydrocarbon plume was found to comprise ~70 km2 and extended beyond study area. The plume width narrowed from 3 km near the source to 0.7 km further from the source, and then expanded to 6.7 km at the edge of the study area. This pattern matches the cyclonic gyre which is the normal current flow in this part of the Santa Barbara Channel - pushing water to the shore near the seep field and then broadening the plume while the water turns offshore further from the source. Concentrations of gaseous hydrocarbons decrease as the plume migrates. Time series sampling shows similar plume width and hydrocarbon concentrations when normal current conditions prevail. In contrast, smaller plume width and low hydrocarbon concentrations were observed when an additional anticyclonic eddy reversed the normal current flow, and a much broader plume with higher hydrocarbon concentrations was observed during a time of diminished speed within the current gyre. These results demonstrate that surface currents control hydrocarbon plume dynamics in the SBC, though hydrocarbon flux to the atmosphere is likely less dependent on currents. Estimates of air- sea hydrocarbon flux and biological oxidation rates will also be presented.

  8. Things fall apart: Fragmentation reactions in the oxidative aging of organic species

    Science.gov (United States)

    Kroll, J. H.; Isaacman-VanWertz, G. A.; Wilson, K. R.; Daumit, K. E.; Kessler, S. H.; Lim, C. Y.; Worsnop, D. R.

    2016-12-01

    The atmospheric oxidation of organic compounds involves a wide array of chemical transformations, including functionalization reactions (addition of polar functional groups to the carbon skeleton), fragmentation reactions (formation of lower carbon-number products via C-C bond scission), and accretion reactions (increases in molecular weight by the combination of two chemical species). Each of these reaction classes can lead to large changes in volatility, and hence can have major implications for atmospheric organic aerosol (OA). For example, the formation of OA is predominantly driven by functionalization and accretion reactions, which generally lead to decreases in volatility. Here we describe a series of laboratory studies of the subsequent organic "aging", the multiday oxidation processes that occur after the initial OA formation and growth. In these studies, the multigenerational oxidation of organic compounds in various phases (the gas phase, the condensed OA phase, and the aqueous phase) is carried out within either an environmental chamber or a flow reactor, and monitored using various high-resolution mass spectrometric techniques. In all cases it is found that fragmentation reactions play a major role in the observed aging chemistry, dominated by the formation of small, volatile oxidation products. These results suggest that multi-day oxidative aging processes do not lead to sustained aerosol growth, but rather may serve as a chemical sink for atmospheric OA.

  9. Process for refining hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Risenfeld, E H

    1924-11-26

    A process is disclosed for the refining of hydrocarbons or other mixtures through treatment in vapor form with metal catalysts, characterized by such metals being used as catalysts, which are obtained by reduction of the oxide of minerals containing the iron group, and by the vapors of the hydrocarbons, in the presence of the water vapor, being led over these catalysts at temperatures from 200 to 300/sup 0/C.

  10. Method for upgrading diene-containing hydrocarbon mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Kidwell, L.E. Jr.; Holcomb, D.E.

    1984-05-22

    There is disclosed a method for upgrading of hydrocarbon mixtures, so as to reduce their content of gum precursors such as diolefins and pseudo-diolefins, and provide a resulting product mixture suitable for mild hydrogenation, for use as a motor fuel or as a feed stock to an extraction unit. The process comprises obtaining a hydrocarbon mixture containing about 60-90 wt. % of aromatic components, about 3-40 wt. % of dienes and pseudodienes, and monoolefins, and up to about 6 wt. % of relatively unreactive organic compounds, reacting this mixture with elemental sulfur in the approximate weight ratio of about 5-95 wt. % of the hydrocarbon mixture with about 95-5 wt. % of elemental sulfur, the reaction being carried out at a temperature in the range of 100/sup 0/-150/sup 0/ C. for about 10 minutes to 24 hours with good mixing, removing the unreacted materials by distillation and separating a sulfur-hydrocarbon reaction product to provide the upgraded hydrocarbon mixture.

  11. Identification and characterization of epoxide hydrolase activity of polycyclic aromatic hydrocarbon-degrading bacteria for biocatalytic resolution of racemic styrene oxide and styrene oxide derivatives.

    Science.gov (United States)

    Woo, Jung-Hee; Kwon, Tae-Hyung; Kim, Jun-Tae; Kim, Choong-Gon; Lee, Eun Yeol

    2013-04-01

    A novel epoxide hydrolase (EHase) from polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was identified and characterized. EHase activity was identified in four strains of PAH-degrading bacteria isolated from commercial gasoline and oil-contaminated sediment based on their growth on styrene oxide and its derivatives, such as 2,3- and 4-chlorostyrene oxides, as a sole carbon source. Gordonia sp. H37 exhibited high enantioselective hydrolysis activity for 4-chlorostyrene oxide with an enantiomeric ratio of 27. Gordonia sp. H37 preferentially hydrolyzed the (R)-enantiomer of styrene oxide derivatives resulting in the preparation of a (S)-enantiomer with enantiomeric excess greater than 99.9 %. The enantioselective EHase activity was identified and characterized in various PAH-degrading bacteria, and whole cell Gordonia sp. H37 was employed as a biocatalyst for preparing enantiopure (S)-styrene oxide derivatives.

  12. Modification of the performance of WO{sub 3}-ZrO{sub 2} catalysts by metal addition in hydrocarbon reactions

    Energy Technology Data Exchange (ETDEWEB)

    Torres, Gerardo Carlos; Manuale, Debora Laura; Benitez, Viviana Monica; Vera, Carlos Roman; Yori, Juan Carlos, E-mail: jyori@fiq.unl.edu.ar [Instituto de Investigaciones en Catalisis y Petroquimica, Facultad de Ingenieria Quimica, Universidad Nacional del Litoral, Consejo Nacional de Investigaciones Cientifica y Tecnicas, Santiago del Estero Santa Fe (Argentina)

    2012-07-01

    A study of the different hydrocarbon reactions over Ni doped WO{sub 3}-ZrO{sub 2} catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane) increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition. (author)

  13. Kinetics of transuranium element oxidation-reduction reactions in solution

    International Nuclear Information System (INIS)

    Gourisse, D.

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [fr

  14. Direct hydrocarbon fuel cells

    Science.gov (United States)

    Barnett, Scott A.; Lai, Tammy; Liu, Jiang

    2010-05-04

    The direct electrochemical oxidation of hydrocarbons in solid oxide fuel cells, to generate greater power densities at lower temperatures without carbon deposition. The performance obtained is comparable to that of fuel cells used for hydrogen, and is achieved by using novel anode composites at low operating temperatures. Such solid oxide fuel cells, regardless of fuel source or operation, can be configured advantageously using the structural geometries of this invention.

  15. Products obtained after in vitro reaction of 7,12-dimethylbenz[alpha]anthracene 5,6-oxide with nucleic acids.

    Science.gov (United States)

    Blobstein, S H; Weinstein, I B; Grunberger, D; Weisgras, J; Harvey, R G

    1975-07-29

    Several lines of evidence suggest that oxide derivatives of carcinogenic polycyclic hydrocarbons are the reactive intermediates for in vivo binding to cellular nucleic acids. In the present study the covalent binding of 7,12-dimethylbenz[alpha]anthracene 5,6-oxide to synthetic homopolymers and nucleic acids in aqueous-acetone solutions has been investigated. Poly(G) was found to be the most reactive nucleic acid and underwent approximately 7-10% modification. Alkaline hydrolysis of the poly(G)-dimethylbenzathracene conjugate yielded chromatographically distinct polycyclic hydrocarbon-modified nucleotides which were further characterized by spectral analyses and enzymatic and chemical degradation. When the oxide was allowed to react with GMP or dGMP, at least two products were obtained in about 1% yield. Acid hydrolysis of the dGMP-dimethylbenzanthracene conjugates liberated the corresponding guanine-dimethylbenzathracene products. Mass spectral analysis of the modified bases provided direct evidence that we had obtained covalent binding of the poly-cyclic hydrocarbon to guanine. The mass spectral cleavage pattern suggest that one of these products is a hydroxydihydro derivative of dimethylbenzanthracene bound to guanine and the other is a dimethylbenzanthracene-guanine conjugate. Additional structural aspects of these guanine derivatives are discussed.

  16. Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

    Science.gov (United States)

    Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

    2017-01-18

    As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

  17. Electrocatalysis of the hydrogen evolution reaction by rhenium oxides electrodeposited by pulsed-current

    International Nuclear Information System (INIS)

    Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis

    2015-01-01

    Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.

  18. Plasma-catalytic reforming of liquid hydrocarbons

    International Nuclear Information System (INIS)

    Nedybaliuk, O.A.; Chernyak, V.Ya; Kolgan, V.V.; Iukhymenko, V.V.; Solomenko, O.V.; Fedirchyk, I.I.; Martysh, E.V.; Demchina, V.P.; Klochok, N.V.; Dragnev, S.V.

    2015-01-01

    The series of experiments studying the plasma-catalytic reforming of liquid hydrocarbons was carried out. The dynamic plasma-liquid system based on a low-power rotating gliding arc with solid electrodes was used for the investigation of liquid hydrocarbons reforming process. Conversion was done via partial oxidation. A part of oxidant flow was activated by the discharge. Synthesis-gas composition was analysed by means of mass-spectrometry and gas-chromatography. A standard boiler, which operates on natural gas and LPG, was used for the burning of synthesis-gas

  19. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  20. Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    1927-02-22

    Coal tar, mineral oils, bitumens, coal extraction products, hydrogenation products of coal, oil schists can be atomized and heated with steam to decompose pyrogenetically and form gases rich in olefins which may be heated with or without pressure and with or without catalysts to produce liquid hydrocarbons of low boiling point, some of which may be aromatic. The apparatus should be lined with copper, silica, or ferrosilicon to prevent contact of the bases with iron which causes deposition of soot. Catalysts used may be metal oxides, silica, graphite, active charcoal, mica, pumice, porcelain, barium carbonate, copper, silver, gold, chromium, boron, or their compounds. At temperatures from 300 to 400/sup 0/C, olefins are produced. At higher temperatures, naphthenes and benzene hydrocarbons are produced.

  1. CORONA-INDUCED PHOTOXIDATION OF ALCOHOLS AND HYDROCARBONS OVER TIO2 IN THE ABSENCE OF A UV LIGHT SOURCE - A NOVEL AND ENVIRONMENTALLY FRIENDLY METHOD FOR OXIDATION

    Science.gov (United States)

    Corona-induced photooxidation is a novel oxidation methodology for the efficient oxidation of alcohols and hydrocarbons utilizing the advantage of both the high oxidizing power of ozone formed in the reactor as well as the photooxidation capability of the UV light generated durin...

  2. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  3. Fuel processor integrated H{sub 2}S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, T.H.; Berry, D.A.; Lyons, K.D.; Beer, S.K.; Freed, A.D. [U.S. Department of Energy, Morgantown, WV (USA). National Energy Technology Laboratory

    2002-12-01

    H{sub 2}S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O{sub 2}-blown coal-derived synthesis gas. The H{sub 2}S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H{sub 2}S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H{sub 2}S and 0.3 order in O{sub 2}. 18 refs., 14 figs., 3 tabs.

  4. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  5. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  6. Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Aghamammadova S.

    2016-01-01

    Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

  7. Methanol conversion to hydrocarbons using modified clinoptilolite catalysts. Investigation of catalyst lifetime and reactivation

    Energy Technology Data Exchange (ETDEWEB)

    Hutchings, G J; Themistocleous, T; Copperthwaite, R G

    1988-10-17

    A study of the deactivation and reactivation of modified clinoptilolite catalysts for methanol conversion to hydrocarbons is reported. Clinoptilolite catalysts, modified by either ammonium ion exchange or hydrochloric acid treatment, exhibit a short useful catalyst lifetime for this reaction (ca. 2-3 h) due to a high rate of coke deposition (3-5.10/sup -3/ g carbon/g catalyst/h). A comparative study of reactivation using oxygen, nitrous oxide and ozone/oxygen as oxidants indicated that nitrous oxide reactivation gives improved catalytic performance when compared to the activity and lifetime of the fresh catalyst. Both oxygen and ozone/oxygen were found to be ineffective for the reactivation of clinoptilolite. Initial studies of in situ on-line reactivation are also described. 3 figs., 15 refs., 4 tabs.

  8. A simple one-step chemistry model for partially premixed hydrocarbon combustion

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Tarrazo, Eduardo [Instituto Nacional de Tecnica Aeroespacial, Madrid (Spain); Sanchez, Antonio L. [Area de Mecanica de Fluidos, Universidad Carlos III de Madrid, Leganes 28911 (Spain); Linan, Amable [ETSI Aeronauticos, Pl. Cardenal Cisneros 3, Madrid 28040 (Spain); Williams, Forman A. [Department of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, CA 92093-0411 (United States)

    2006-10-15

    This work explores the applicability of one-step irreversible Arrhenius kinetics with unity reaction order to the numerical description of partially premixed hydrocarbon combustion. Computations of planar premixed flames are used in the selection of the three model parameters: the heat of reaction q, the activation temperature T{sub a}, and the preexponential factor B. It is seen that changes in q with equivalence ratio f need to be introduced in fuel-rich combustion to describe the effect of partial fuel oxidation on the amount of heat released, leading to a universal linear variation q(f) for f>1 for all hydrocarbons. The model also employs a variable activation temperature T{sub a}(f) to mimic changes in the underlying chemistry in rich and very lean flames. The resulting chemistry description is able to reproduce propagation velocities of diluted and undiluted flames accurately over the whole flammability limit. Furthermore, computations of methane-air counterflow diffusion flames are used to test the proposed chemistry under nonpremixed conditions. The model not only predicts the critical strain rate at extinction accurately but also gives near-extinction flames with oxygen leakage, thereby overcoming known predictive limitations of one-step Arrhenius kinetics. (author)

  9. Enhancement of nitrite on heme-induced oxidative reactions: A potential toxicological implication.

    Science.gov (United States)

    Lu, Naihao; Chen, Wei; Zhu, Jingjie; Peng, Yi-Yuan

    2012-02-01

    Evidence to support the role of heme as major inducers of oxidative damage is increasingly present. Nitrite (NO(2)(-)) is one of the major end products of NO metabolism. Although the biological significance of heme/NO(2)(-)-mediated protein tyrosine nitration is a subject of great interest, the important roles of NO(2)(-) on heme-dependent redox reaction have been greatly underestimated. In this study, we investigated the influence of NO(2)(-) on heme -dependent oxidative reactions. It was found that NO(2)(-) had the capacity to act as a reducing agent to remove high oxidation states of heme iron. In the reduction of ferryl heme to ferric heme, NO(2)(-) was oxidized to a nitrating agent NO(2), and subsequently, tyrosine residues in bovine serum albumin (BSA) were nitrated. However, the presence of NO(2)(-) surprisingly exerted pro-oxidant effect on heme-H(2)O(2)-induced formation of BSA carbonyls at lower concentrations and enhanced the loss of HepG2 cell viability dose-dependently, which was probably due to the ability of this inorganic compound to efficiently enhance the peroxidase activity and oxidative degradation of heme. These data provide novel evidence that the dietary intake and experimental use of NO(2)(-) in vivo and in vitro would possess the pro-oxidant activity through interfering in heme-dependent oxidative reactions. Besides the classic role in protein tyrosine nitration, the deleterious effects on heme redox reactions may provide new insights into the toxicological implications of NO(2)(-) with cellular heme proteins. Copyright © 2011 Elsevier Ltd. All rights reserved.

  10. Theoretical investigation of the reaction of Mn+ with ethylene oxide.

    Science.gov (United States)

    Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

    2012-01-12

    The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

  11. Application of persulfate to remediate petroleum hydrocarbon-contaminated soil: feasibility and comparison with common oxidants.

    Science.gov (United States)

    Yen, Chia-Hsien; Chen, Ku-Fan; Kao, Chih-Ming; Liang, Shu-Hao; Chen, Ting-Yu

    2011-02-28

    In this study, batch experiments were conducted to evaluate the feasibility of petroleum-hydrocarbon contaminated soil remediation using persulfate oxidation. Various controlling factors including different persulfate and ferrous ion concentrations, different oxidants (persulfate, hydrogen peroxide, and permanganate), and different contaminants (diesel and fuel oil) were considered. Results show that persulfate oxidation is capable of treating diesel and fuel oil contaminated soil. Higher persulfate and ferrous ion concentrations resulted in higher diesel degrading rates within the applied persulfate/ferrous ion molar ratios. A two-stage diesel degradation was observed in the batch experiments. In addition, treatment of diesel-contaminated soil using in situ metal mineral activation under ambient temperature (e.g., 25°C) may be a feasible option for site remediation. Results also reveal that persulfate anions could persist in the system for more than five months. Thus, sequential injections of ferrous ion to generate sulfate free radicals might be a feasible way to enhance contaminant oxidation. Diesel oxidation efficiency and rates by the three oxidants followed the sequence of hydrogen peroxide>permanganate>persulfate in the limited timeframes. Results of this study indicate that the application of persulfate oxidation is a feasible method to treat soil contaminated by diesel and fuel oil. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Mn(II) oxidation in Fenton and Fenton type systems : Identification of Reaction Efficiency and Reaction Products

    NARCIS (Netherlands)

    van Genuchten, C.M.; Peña, Jasquelin

    2017-01-01

    Efficient and low-cost methods of removing aqueous Mn(II) are required to improve the quality of impacted groundwater supplies. In this work, we show that Fe(0) electrocoagulation (EC) permits the oxidative removal of Mn(II) from solution by reaction with the reactive oxidant species produced

  13. Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

    Science.gov (United States)

    Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

    2011-11-01

    By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

  14. Sulphation reactions of oxidic dust particles in waste heat boiler environment. Literature review

    Energy Technology Data Exchange (ETDEWEB)

    Ranki, T.

    1999-09-01

    Sulphation of metal oxides has an important role in many industrial processes. In different applications sulphation reactions have different aims and characteristics. In the flash smelting process sulphation of oxidic flue dust is a spontaneous and inevitable phenomena, which takes place in the waste heat boiler (WHB) when cooling down hot dust laden off-gases from sulphide smelters. Oxidic dust particles (size 0 - 50 {mu}m) react with O{sub 2} and SO{sub 2} or SO{sub 3} in a certain temperature range (500 - 800 deg C). Sulphation reactions are highly exothermic releasing large amount of heat, which affects the gas cooling and thermal performance of the boiler. Thermodynamics and kinetics of the system have to be known to improve the process and WHB operation. The rate of sulphation is affected by the prevailing conditions (temperature, gas composition) and particle size and microstructure (porosity, surface area). Some metal oxides (CuO) can react readily with SO{sub 2} and O{sub 2} and act as self-catalysts, but others (NiO) require the presence of an external catalyst to enhance the SO{sub 3} formation and sulphation to proceed. Some oxides (NiO) sulphate directly, some (CuO) may form first intermediate phases (basic sulphates) depending on the reaction conditions. Thus, the reaction mechanisms are very complex. The aim of this report was to search information about the factors affecting the dust sulphation reactions and suggested reaction mechanisms and kinetics. Many investigators have studied sulphation thermodynamics and reaction kinetics and mechanisms of macroscopical metal oxide pieces, but only few articles have been published about sulphation of microscopical particles, like dust. All the found microscale studies dealt with sulphation reactions of calcium oxide, which is not present in the flash smelting process, but used as an SO{sub 2} absorbent in the combustion processes. However, also these investigations may give some hints about the sulphation

  15. Reactions of stabilized Criegee Intermediates

    Science.gov (United States)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  16. An investigation of oxidation products and SOA yields from OH + pesticide reactions

    Science.gov (United States)

    Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

  17. New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

    Directory of Open Access Journals (Sweden)

    Georgiy B. Shul’pin

    2016-03-01

    Full Text Available This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst. Works of recent years (mainly 2010–2016 devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon–hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

  18. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.

    2014-04-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

  19. The oxidative burst reaction in mammalian cells depends on gravity.

    Science.gov (United States)

    Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

    2013-12-20

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

  20. Iron(III Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions

    Directory of Open Access Journals (Sweden)

    Susana L. H. Rebelo

    2016-04-01

    Full Text Available Iron(III fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H2TPFPP and the corresponding iron complex [Fe(TPFPPCl], and the use of [Fe(TPFPPCl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPPCl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(IIIporphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide and green solvent (ethanol. Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

  1. Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

    Science.gov (United States)

    Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

    2016-04-12

    Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

  2. Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

    Science.gov (United States)

    Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

    2000-12-01

    Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

  3. Cuprous oxide nanoparticles dispersed on reduced graphene oxide as an efficient electrocatalyst for oxygen reduction reaction.

    Science.gov (United States)

    Yan, Xiao-Yan; Tong, Xi-Li; Zhang, Yue-Fei; Han, Xiao-Dong; Wang, Ying-Yong; Jin, Guo-Qiang; Qin, Yong; Guo, Xiang-Yun

    2012-02-11

    Cuprous oxide (Cu(2)O) nanoparticles dispersed on reduced graphene oxide (RGO) were prepared by reducing copper acetate supported on graphite oxide using diethylene glycol as both solvent and reducing agent. The Cu(2)O/RGO composite exhibits excellent catalytic activity and remarkable tolerance to methanol and CO in the oxygen reduction reaction. This journal is © The Royal Society of Chemistry 2012

  4. Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

    Science.gov (United States)

    Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

    2011-01-01

    Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

  5. Selection of Suitable Microorganism for Biocatalytic Oxidation Reaction of Racemic Propranolol

    Directory of Open Access Journals (Sweden)

    Rahime SONGÜR

    2017-12-01

    Full Text Available Propranolol is one of the β-blockers which are pharmaceutically important, especially used for treatment of cardiovasculer disease. In this study, the production of enantiomerically pure propranolol was aimed via biocatalytic deracemization including tandem oxidation-reduction reactions of racemic propranolol. Within this content, firstly suitable microorganism for the oxidation of racemic propranolol was investigated. Alcohol dehydrogenase (ADH enzyme for oxidation of propranolol and NADH oxidase enzyme for cofactor regeneration were necessary for the oxidation reactions. For this reason, ADH and NADH oxidase enzymes activities of different microorganisms were measured to select the microorganism for using as enzyme source. These microorganisms are Lactobacillus kefir NRRL B-1839, Rhodotorula glutunis DSM 70398, Rhizopus oryzae CBS 111718, Rhizopus arhizus. The highest ADH and NADH oxidase activities were obtained for L. kefir.

  6. Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

    Science.gov (United States)

    Fox, D. S.

    1994-01-01

    Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

  7. Kinetic particularities of strained alicyclic compounds formation in catalytic methanol to hydrocarbon transformation process

    OpenAIRE

    Doluda V.; Brovko R.; Giniatullina N.; Sulman M.

    2017-01-01

    The catalytic transformation of methanol into hydrocarbons is a complex chemical process, accompanied by chain parallel chemical transformation reactions. The most valuable products of the methanol to hydrocarbons catalytic transformation reaction are the strained hydrocarbons — cyclopropane derivatives. These compounds can be used as a high-energy fuel, and also as a valuable chemical raw material. However, the yield of strained compounds in methanol to hydrocarbons catalytic transformation ...

  8. Radiolysis of hydrocarbons in liquid phase (Modern state of problem)

    International Nuclear Information System (INIS)

    Saraeva, V.V.

    1986-01-01

    Problems of ionizing radiation effect on hydrocarbons and hydrocarbon systems in a liquid phase are considered. Modern representations on the mechanism of hydrocarbon radiolysis are presented. Electron moderation and ion-electron pair formation, behaviour of charged particles, excited states, radical formation and their reactions are discussed. Behaviour of certain hydrocarbon classes: alkanes, cyclic hydrocarbons, olefines, aromatic hydrocarbons as well as different hydrocarbon mixtures is considered in detail. Radiation-chemical changes in organic coolants and ways of increasing radiation resistance are considered. Polyphenyl compounds are noted to be most perspective here

  9. Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

    Science.gov (United States)

    Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

    2017-06-01

    Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

  10. Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

    Science.gov (United States)

    Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

    2018-02-16

    A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Motor fuels by hydrogenation of liquid hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    1938-05-07

    A process is disclosed for the production of knock-stable low-boiling motor fuels by conversion of liquid hydrocarbons which are vaporizable under the reaction conditions, which comprises passing the initial material at a temperature above 380/sup 0/C in a true vapor phase under pressure of more than 40 atmospheres together with hydrogen and gaseous hydrocarbons containing more than 1 carbon atom in the molecule in an amount by volume larger than that of the hydrogen over catalysts stable to poisoning stationarily confined in the reaction vessel.

  12. Mass transfer model for two-layer TBP oxidation reactions: Revision 1

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

  13. Reaction selectivity studies on nanolithographically-fabricated platinum model catalyst arrays

    Energy Technology Data Exchange (ETDEWEB)

    Grunes, Jeffrey Benjamin [Univ. of California, Berkeley, CA (United States)

    2004-05-01

    In an effort to understand the molecular ingredients of catalytic activity and selectivity toward the end of tuning a catalyst for 100% selectivity, advanced nanolithography techniques were developed and utilized to fabricate well-ordered two-dimensional model catalyst arrays of metal nanostructures on an oxide support for the investigation of reaction selectivity. In-situ and ex-situ surface science techniques were coupled with catalytic reaction data to characterize the molecular structure of the catalyst systems and gain insight into hydrocarbon conversion in heterogeneous catalysis. Through systematic variation of catalyst parameters (size, spacing, structure, and oxide support) and catalytic reaction conditions (hydrocarbon chain length, temperature, pressures, and gas composition), the data presented in this dissertation demonstrate the ability to direct a reaction by rationally adjusting, through precise control, the design of the catalyst system. Electron beam lithography (EBL) was employed to create platinum nanoparticles on an alumina (Al2O3) support. The Pt nanoparticle spacing (100-150-nm interparticle distance) was varied in these samples, and they were characterized using x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), both before and after reactions. The TEM studies showed the 28-nm Pt nanoparticles with 100 and 150-nm interparticle spacing on alumina to be polycrystalline in nature, with crystalline sizes of 3-5 nm. The nanoparticle crystallites increased significantly after heat treatment. The nanoparticles were still mostly polycrystalline in nature, with 2-3 domains. The 28-nm Pt nanoparticles deposited on alumina were removed by the AFM tip in contact mode with a normal force of approximately 30 nN. After heat treatment at 500 C in vacuum for 3 hours, the AFM tip, even at 4000 nN, could not remove the platinum

  14. Kinetics of reactions of chromium, molybdenum and tungsten hexacarbonyls with hydroxylamine and trimethylamine oxide

    International Nuclear Information System (INIS)

    Maksakov, V.A.; Ershova, V.A.

    1994-01-01

    Mechanism of M(CO) 6 (M = Cr, Mo, W) reaction with hydroxylamine was studied. On the basis of kinetic data it was ascertained that as a result of the reaction CO oxidation to CO 2 and intramolecular transfer of amine formed to the central atom of metal occur. Mechanisms of M(CO) 6 reactions with hydroxylamine and trimethylamine oxide are compared

  15. Recovery of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1941-02-10

    A process is disclosed for recovery of hydrocarbon oils, especially lubricating oils or diesel oils, through pressure hydrogenation of distillation, extraction of hydrogenation products from coal or coaly materials or from oils such as mineral oils or tars in liquid phase by use in a reaction vessel of fixed-bed catalysts, characterized in that as starting material is employed material which has been freed of asphaltic and resinous material by hydrogenation refining, vacuum-steam distillation, treatment with hydrogen-rich hydrocarbons (hydroforming), or sulfuric acid.

  16. A shock tube and laser absorption study of ignition delay times and OH reaction rates of ketones: 2-Butanone and 3-buten-2-one

    KAUST Repository

    Badra, Jihad; Elwardani, Ahmed Elsaid; Khaled, Fathi; Vasu, Subith S.; Farooq, Aamir

    2014-01-01

    Ketones are potential biofuel candidates and are also formed as intermediate products during the oxidation of large hydrocarbons or oxygenated fuels, such as alcohols and esters. This paper presents shock tube ignition delay times and OH reaction

  17. Model studies in hydrocarbon oxidation. Progress report, April 1--November 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Parkin, G.

    1993-12-31

    The research performed during the period 1 April--31 November 1993 has centered on an investigation of the chemistry of molecular terminal oxo complexes. In the long term, it is hoped that this research will provide results that are relevant to systems concerned with hydrocarbon oxidation. The authors have also carried studies of transition metal complexes that contain terminal sulfido, selenido and tellurido ligands, since a knowledge of the chemistry of the heavier congeners of this group will help provide a more complete understanding of the chemistry of transition metal oxo complexes. Furthermore, the chemistry of the metal sulfido derivatives will be directly related to hydrodesulfurization, an extremely important industrial process, for which transition metal-sulfido derivatives, e.g. MoS{sub 2}, are active catalysts.

  18. Effect of magnetic field on the zero valent iron induced oxidation reaction

    International Nuclear Information System (INIS)

    Kim, Dong-hyo; Kim, Jungwon; Choi, Wonyong

    2011-01-01

    Highlights: → We investigate the zero valent iron induced oxidation in the presence of magnetic field. → The oxidative degradation of 4-chlorophenol is enhanced by the magnetic field. → ESR measurement confirms that more OH radicals are generated in the presence of magnetic field. → The magnetic field affects the mass transfer of O 2 and the recombination of radicals. - Abstract: The magnetic field (MF) effect on the zero valent iron (ZVI) induced oxidative reaction was investigated for the first time. The degradation of 4-chlorophenol (4-CP) in the ZVI system was employed as the test oxidative reaction. MF markedly enhanced the degradation of 4-CP with the concurrent production of chlorides. The consumption of dissolved O 2 by ZVI reaction was also enhanced in the presence of MF whereas the competing reaction of H 2 production from proton reduction was retarded. Since the ZVI-induced oxidation is mainly driven by the in situ generated hydroxyl radicals, the production of OH radicals was monitored by the spin trap method using electron spin resonance (ESR) spectroscopy. It was confirmed that the concentration of trapped OH radicals was enhanced in the presence of MF. Since both O 2 and Fe 0 are paramagnetic, the diffusion of O 2 onto the iron surface might be accelerated under MF. The magnetized iron can attract oxygen on itself, which makes the mass transfer process faster. As a result, the surface electrochemical reaction between Fe 0 and O 2 can be accelerated with the enhanced production of OH radicals. MF might retard the recombination of OH radicals as well.

  19. [Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

    Science.gov (United States)

    Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

    1998-04-01

    In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

  20. Heterogeneous reactions of carbonyl sulfide on mineral oxides: mechanism and kinetics study

    Directory of Open Access Journals (Sweden)

    Y. Liu

    2010-11-01

    Full Text Available The heterogeneous reactions of carbonyl sulfide (OCS on the typical mineral oxides in the mineral dust particles were investigated using a Knudsen cell flow reactor and a diffuse reflectance UV-vis spectroscopy. The reaction pathway for OCS on mineral dust was identified based on the gaseous products and surface species. The hydrolysis of OCS and succeeding oxidation of intermediate products readily took place on α-Al2O3, MgO, and CaO. Reversible and irreversible adsorption of OCS were observed on α-Fe2O3 and ZnO, respectively, whereas no apparent uptake of OCS by SiO2 and TiO2 was observed. The reactivity of OCS on these oxides depends on both the basicity of oxides and the decomposition reactivity of oxides for H2S. Based on the individual uptake coefficients and chemical composition of authentic mineral dust, the uptake coefficient (γBET of mineral dust was estimated to be in the range of 3.84×10−7–2.86×10−8. The global flux of OCS due to heterogeneous reactions and adsorption on mineral dust was estimated at 0.13–0.29 Tg yr−1, which is comparable to the annual flux of OCS for its reaction with ·OH.

  1. Graphene oxide bonded fused-silica fiber for solid-phase microextraction-gas chromatography of polycyclic aromatic hydrocarbons in water.

    Science.gov (United States)

    Xu, Lili; Feng, Juanjuan; Li, Jubai; Liu, Xia; Jiang, Shengxiang

    2012-01-01

    A novel chemically bonded graphene oxide/fused-silica fiber was prepared and applied in solid-phase microextraction of six polycyclic aromatic hydrocarbons from water samples coupled with gas chromatography. It exhibited high extraction efficiency and excellent stability. Effects of extraction time, extraction temperature, ionic strength, stirring rate and desorption conditions were investigated and optimized in our work. Detection limits to the six polycyclic aromatic hydrocarbons were less than 0.08 μg/L, and their calibration curves were all linear (R(2)≥0.9954) in the range from 0.05 to 200 μg/L. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.13 and 15.87%, respectively. This novel fiber was then utilized to analyze two real water samples from the Yellow River and local waterworks, and the recoveries of samples spiked at 1 and 10 μg/L ranged from 84.48 to 118.24%. Compared with other coating materials, this graphene oxide-coated fiber showed many advantages: wide linear range, low detection limit, and good stability in acid, alkali, organic solutions and at high temperature. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

    2011-01-01

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

  3. Production of hydrocarbons of value

    Energy Technology Data Exchange (ETDEWEB)

    1931-06-16

    A process is described for the production of hydrocarbons of great value by treating with heat and pressure carbonaceous materials such as coals, tars, mineral oils, and products of distillation and transformation of these materials, also for the refining with heat and pressure of mixed liquid hydrocarbons by means of hydrogen gas, preferably in the presence of catalysts, consisting in using as the hydrogenating gas that obtained by gasification of combustible solids after partial or complete cleaning at atmospheric or elevated pressures, by means of solid adsorbents, chemical agents or catalysts, or mixtures of these agents, the hydrocarbons being characterized by strong unsaturation, and the presence of oxygen, sulfur compounds, and oxides of nitrogen.

  4. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

    Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  5. Direct electroreduction of CO2 into hydrocarbon

    International Nuclear Information System (INIS)

    Winea, Gauthier; Ledoux, Marc-Jacques; Pham-Huu, Cuong; Gangeri, Miriam; Perathoner, Siglinda; Centi, Gabriele

    2006-01-01

    A lot of methods exist to directly reduce carbon dioxide into hydrocarbons: the photoelectrochemical process is certainly the most interesting, essentially due to the similarities with photosynthesis. As the human activities produce a great quantity of CO 2 , this one can then be considered as an infinite source of carbon. The products of this reaction are identical to those obtained during a Fischer-Tropsch reaction, that is to say hydrocarbons, alcohols and carboxylic acids. These works deal with the electrochemical reduction of CO 2 in standard conditions of temperature and pressure. The photochemical part has been replaced by a current generator as electrons source and a KHCO 3 aqueous solution as protons source. The first catalytic results clearly show that it is possible to reduce CO 2 into light hydrocarbons, typically from C1 to C9. (O.M.)

  6. Process of converting phenols into hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Seelig, S

    1929-02-02

    A process is disclosed for the conversion of phenols into hydrocarbons, characterized by preheating a mixture of phenols and hydrogen or hydrogen-producing gases to approximately the reaction temperature under pressure, heating by passage percussion-like through a bath of metal to the reaction temperature, and rapidly cooling.

  7. Process for treating hydrocarbons, etc

    Energy Technology Data Exchange (ETDEWEB)

    1933-09-15

    A process is described for treating simultaneously bituminous substances and hydrocarbon oils for the production of low-boiling hydrocarbons and volatilization of the bituminous substances, characterized by the fact that it consists of heating a current of charge constituted by a mixture of the bituminous substances and hydrocarbon oils, to a high temperature, passing the heated current into a zone of extended reaction where the vapors are separated from the liquid or solid residue to favor transformation of the liquid hydrocarbons and volatilization of the bituminous substances, owing to the utilization of a heating agent carried to a high temperature being brought in contact with the heated charge in order to communicate its heat to the charge, while this later presents itself as relatively fine pellet or in the condition of distinct particles, particularly separated from one another.

  8. A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

    Science.gov (United States)

    Helgeson, Harold C.; Richard, Laurent; McKenzie, William F.; Norton, Denis L.; Schmitt, Alexandra

    2009-02-01

    Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ≳25 but ≲100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ˜1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO 2 gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO 2 gas, and a more mature (oxidized) kerogen with a lower

  9. Hydrocarbon formation mechanism during uranium monocarbide hydrolysis

    International Nuclear Information System (INIS)

    Ermolaev, M.I.; Tishchenko, G.V.

    1979-01-01

    The hydrolysis of uranium monocarbide in oxidative media and in the presence of excessive hydrogen in statu nascendi has been investigated. It was found that oxydants promote the formation of elementary carbon, while in the presence of hydrogen the yield of light C-C hydrocarbons increases. EPR data confirm the radical mechanism of hydrocarbons formation during the decomposition of uranium monocarbide

  10. Innocuous oil as an additive for reductive reactions involving zero valence iron

    International Nuclear Information System (INIS)

    Cary, J.W.; Cantrell, K.J.

    1994-11-01

    Reductive reactions involving zero valence iron appear to hold promise for in situ remediation of sites containing chlorinated hydrocarbon solvents and certain reducible metals and radionuclides. Treatment involves the injection of metallic iron and the creation of low levels of dissolved oxygen in the aqueous phase through oxidation of the metallic iron. The use of a biodegradable immiscible and innocuous organic liquid such as vegetable oil as an additive offers several intriguing possibilities. The oil phase creates a large oil-water interface that is immobile with respect to flow in the aqueous phase. This phase will act as a trap for chlorinated hydrocarbons and could potentially increase the reaction efficiency of reductive dehalogenation of chlorinated hydrocarbons by the metallic iron. When iron particles are suspended in the oil before injection they are preferentially held in the oil phase and tend to accumulate at the oil-water interface. Thus oil injection can serve as a mechanism for creating a stable porous curtain of metallic iron in the vadose to maintain a low oxygen environment which will minimize the consumption of the iron by molecular oxygen

  11. Selective catalytic oxidation of hydrocarbons as a challenge to the chemical engineer

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G [Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Lehrstuhl fuer Technische Chemie 1

    1978-08-01

    Selective catalytic oxidation is beginning to play a more and more significant role in the process of converting the most important chemical raw materials, crude oil and natural gas, into intermediate and end products. In many cases, this technique makes it possible to replace old processes consisting of many steps by more economical single-step reactions. The typical example of oxidation or ammoxidation of propylene demonstrates the problems which must be solved by the chemical engineer during the development of a heterogeneous catalytic oxidation process. The particular importance of a systematic development of a catalyst is emphasized. General aspects relating to the design of new catalytic processes, or the improvement of existing ones are also discussed.

  12. Difference in chemical reactions in bulk plasma and sheath regions during surface modification of graphene oxide film using capacitively coupled NH{sub 3} plasma

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sung-Youp; Kim, Chan; Kim, Hong Tak, E-mail: zam89blue@gmail.com [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2015-09-14

    Reduced graphene oxide (r-GO) films were obtained from capacitively coupled NH{sub 3} plasma treatment of spin-coated graphene oxide (GO) films at room temperature. Variations were evaluated according to the two plasma treatment regions: the bulk plasma region (R{sub bulk}) and the sheath region (R{sub sheath}). Reduction and nitridation of the GO films began as soon as the NH{sub 3} plasma was exposed to both regions. However, with the increase in treatment time, the reduction and nitridation reactions differed in each region. In the R{sub bulk}, NH{sub 3} plasma ions reacted chemically with oxygen functional groups on the GO films, which was highly effective for reduction and nitridation. While in the R{sub sheath}, physical reactions by ion bombardment were dominant because plasma ions were accelerated by the strong electrical field. The accelerated plasma ions reacted not only with the oxygen functional groups but also with the broken carbon chains, which caused the removal of the GO films by the formation of hydrocarbon gas species. These results showed that reduction and nitridation in the R{sub bulk} using capacitively coupled NH{sub 3} plasma were very effective for modifying the properties of r-GO films for application as transparent conductive films.

  13. Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions.

    Science.gov (United States)

    Mailloux, Ryan J; Jin, Xiaolei; Willmore, William G

    2014-01-01

    Mitochondria have a myriad of essential functions including metabolism and apoptosis. These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS). The production of ATP and ROS are intimately linked to the electron transport chain (ETC). Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP. Electron transfer through the respiratory chain and nutrient oxidation also produces ROS. At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death. However, if maintained at low enough concentrations ROS can serve as important signaling molecules. Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production. Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes. Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion. We also consider the chemistry behind these reactions and how they are modulated in mitochondria. In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling.

  14. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C4H5, from reaction of C(3Pj) with propylene, C3H6 (X1A)

    International Nuclear Information System (INIS)

    Kaiser, R.I.; Stranges, D.; Bevsek, H.M.; Lee, Y.T.; Suits, A.G.

    1997-01-01

    The reaction between ground state carbon atoms and propylene, C 3 H 6 , was studied at average collision energies of 23.3 and 45.0 kJmol -1 using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C 4 H 5 at m/e=53 were recorded. Forward-convolution fitting of the data yields a maximum energy release as well as angular distributions consistent with the formation of methylpropargyl radicals. Reaction dynamics inferred from the experimental results suggest that the reaction proceeds on the lowest 3 A surface via an initial addition of the carbon atom to the π-orbital to form a triplet methylcyclopropylidene collision complex followed by ring opening to triplet 1,2-butadiene. Within 0.3 endash 0.6 ps, 1,2-butadiene decomposes through carbon endash hydrogen bond rupture to atomic hydrogen and methylpropargyl radicals. The explicit identification of C 4 H 5 under single collision conditions represents a further example of a carbon endash hydrogen exchange in reactions of ground state carbon with unsaturated hydrocarbons. This versatile machine represents an alternative pathway to build up unsaturated hydrocarbon chains in combustion processes, chemical vapor deposition, and in the interstellar medium. copyright 1997 American Institute of Physics

  15. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    International Nuclear Information System (INIS)

    Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-01-01

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

  16. Reaction of iodine oxidation by potassium permanganate in tributyl phosphate

    International Nuclear Information System (INIS)

    Khokhlov, M.L.; Legin, E.K.

    1990-01-01

    Stoichiometry was determined and kinetics of iodine oxidation by potassium permanganate in tributylphosphate was studied. Kinetic scheme, which agrees with stoichiometry and experimental kinetic equation of the reaction, is suggested. A mixture is the reaction product. It is ascertained that when the mixture is heated, thermal decomposition of iodate to iodide occurs without elementary iodine separation, which is catalyzed by polymanganate

  17. Conversion of hydrocarbon oils into motor fuels

    Energy Technology Data Exchange (ETDEWEB)

    1937-11-09

    The abstract describes a process for producing lower boiling hydrocarbon motor fuels with a starting material of wide boiling range composed primarily of hydrocarbon oils boiling substantially above the boiling range of the desired product. Separate catalytic and pyrolytic conversion zones are simultaneously maintained in an interdependent relationship. Higher boiling constituents are separated from residual constituents by fractionation while desirable reaction conditions are maintained. All or at least a portion of the products from the catalytic and pyrolytic conversion zones are blended to yield the desired lower boiling hydrocarbons or motor fuels.

  18. The microbial degradation of polycyclic aromatic hydrocarbons in soils and sediments. Der mikrobielle Abbau polyzyklischer aromatischer Kohlenwasserstoffe (PAK) in Boeden und Sedimenten: Mineralisierung, Metabolitenbildung und Entstehung gebundener Rueckstaende

    Energy Technology Data Exchange (ETDEWEB)

    Mahro, B; Kaestner, M [Technische Univ. Hamburg-Harburg (Germany). Arbeitsbereich Biotechnologie 2

    1993-02-01

    The microbial degradation of polycylic aromatic hydrocarbons in soils and sediments: mineralization, metabolite excretion and the formation of bound residues microorganisms degrade polycyclic aromatic hydrocarbons (PAH) via three different metabolic pathways: mineralization, cometabolic oxidation or an unspecific triggering of radical reactions. As a result of these microbial transformation processes PAH may be converted to CO[sub 2] and biomass or partially oxidized metabolites. The possible fate of these presumed metabolites in the soil matrix is analyzed. It is pointed out that the formation of humus bound residues, stimulated by microbial exoenzyme activities, may contribute to significant extent to the disappearance of PAHs in soils and sediments. The relevance of this fact for the biological remediation of contaminated soils is discussed. (orig.).

  19. Controlled nitric oxide production via O(1D  + N2O reactions for use in oxidation flow reactor studies

    Directory of Open Access Journals (Sweden)

    A. Lambe

    2017-06-01

    Full Text Available Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3 is photolyzed at 254 nm to produce O(1D radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA formation pathways. Simple addition of nitric oxide (NO results in fast conversion of NOx (NO + NO2 to nitric acid (HNO3, making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2 radicals as a sink for organic peroxy (RO2 radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D + N2O  →  2NO, followed by the reaction NO + O3  →  NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS measurements with nitrate (NO3− reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

  20. Some reactions of oxidizing radicals with enzymes in aqueous solution

    International Nuclear Information System (INIS)

    Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

    1979-01-01

    A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

  1. Low temperature oxidation of hydrocarbons using an electrochemical reactor

    DEFF Research Database (Denmark)

    Ippolito, Davide

    conversion was a complex function of multiple variables: the microstructure of the backbone, the polarization resistance of the electrodes, both at OCV and under polarization, the electrical and morphological properties of the infiltrated material and the specific reaction conditions like the propene......This study investigated the use of a ceramic porous electrochemical reactor for the deep oxidation of propene. Two electrode composites, La0.85Sr0.15MnO3±d/Ce0.9Gd0.1O1.95 (LSM/CGO) and La0.85Sr0.15FeMnO3/Ce0.9Gd0.1O1.95 (LSF/CGO), were produced in a 5 single cells stacked configuration and used...... prolonged polarization was able to partially counteract the instability of the infiltrated Ce0.9Gd0.1O1.95. This project demonstrated the possibility to enhance the oxidation of propene by polarization in a porous ceramic reactor. The infiltration of different active materials helped to increase...

  2. Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

    Science.gov (United States)

    Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

    2018-03-01

    N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

  3. Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

    International Nuclear Information System (INIS)

    Santos, Elizabeth; Schmickler, Wolfgang

    2008-01-01

    A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

  4. Biotransformation of monoaromatic hydrocarbons under anoxic conditions

    International Nuclear Information System (INIS)

    Ball, H.A.; Reinhard, M.; McCarty, P.L.

    1991-01-01

    Aromatic hydrocarbons contained in gasoline are environmental pollutants of particular concern since they are relatively soluble in water, many are toxic, and some are confirmed carcinogens, (e.g., benzene). Although most gasoline constituents are readily degraded in aerobic surface water systems, the groundwater environment associated with hydrocarbon spills is typically anaerobic, thus precluding aerobic degradation pathways. In the absence of oxygen, degradation of gasoline components can take place only with the utilization of alternate electron acceptors such as nitrate, sulfate, carbon dioxide, and possibly ferric iron or other metal oxides. Benzene, toluene, and xylene isomers were completely degraded by aquifer- or sewage sludge-derived microorganisms under dentrifying and methanogenic conditions. Recently, a pure culture was found to degrade toluene and m-xylene nitrate or nitrous oxide as an electron acceptor. This paper presents initial results of ongoing study to develop and characterize microbial consortia capable of transforming aromatic hydrocarbons under nitrate-reducing conditions, and understand the effect of environmental factors on the biotransformation processes

  5. Microbial consortia involved in the anaerobic degradation of hydrocarbons.

    Science.gov (United States)

    Zwolinski; Harris, R F; Hickey, W J

    2000-01-01

    In this review, we examine the energetics of well-characterized biodegradation pathways and explore the possibilities for these to support growth of multiple organisms interacting in consortia. The relevant phenotypic and/or phylogenetic characteristics of isolates and consortia mediating hydrocarbon degradation coupled with different terminal electron-accepting processes (TEAP) are also reviewed. While the information on metabolic pathways has been gained from the analysis of individual isolates, the energetic framework presented here demonstrates that microbial consortia could be readily postulated for hydrocarbon degradation coupled to any TEAP. Several specialized reactions occur within these pathways, and the organisms mediating these are likely to play a key role in defining the hydrocarbon degradation characteristics of the community under a given TEAP. Comparing these processes within and between TEAPs reveals biological unity in that divergent phylotypes display similar degradation mechanisms and biological diversity in that hydrocarbon-degraders closely related as phylotypes differ in the type and variety of hydrocarbon degradation pathways they possess. Analysis of microcosms and of field samples suggests that we have only begun to reveal the diversity of organisms mediating anaerobic hydrocarbon degradation. Advancements in the understanding of how hydrocarbon-degrading communities function will be significantly affected by the extent to which organisms mediating specialized reactions can be identified, and tools developed to allow their study in situ.

  6. Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

    1984-01-01

    The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

  7. Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Benziger, J.B.; Madix, R.J.

    1980-09-01

    Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

  8. Neutralization of methyl cation via chemical reactions in low-energy ion-surface collisions with fluorocarbon and hydrocarbon self-assembled monolayer films.

    Science.gov (United States)

    Somogyi, Arpád; Smith, Darrin L; Wysocki, Vicki H; Colorado, Ramon; Lee, T Randall

    2002-10-01

    Low-energy ion-surface collisions of methyl cation at hydrocarbon and fluorocarbon self-assembled monolayer (SAM) surfaces produce extensive neutralization of CH3+. These experimental observations are reported together with the results obtained for ion-surface collisions with the molecular ions of benzene, styrene, 3-fluorobenzonitrile, 1,3,5-triazine, and ammonia on the same surfaces. For comparison, low-energy gas-phase collisions of CD3+ and 3-fluorobenzonitrile molecular ions with neutral n-butane reagent gas were conducted in a triple quadrupole (QQQ) instrument. Relevant MP2 6-31G*//MP2 6-31G* ab initio and thermochemical calculations provide further insight in the neutralization mechanisms of methyl cation. The data suggest that neutralization of methyl cation with hydrocarbon and fluorocarbon SAMs occurs by concerted chemical reactions, i.e., that neutralization of the projectile occurs not only by a direct electron transfer from the surface but also by formation of a neutral molecule. The calculations indicate that the following products can be formed by exothermic processes and without appreciable activation energy: CH4 (formal hydride ion addition) and C2H6 (formal methyl anion addition) from a hydrocarbon surface and CH3F (formal fluoride addition) from a fluorocarbon surface. The results also demonstrate that, in some cases, simple thermochemical calculations cannot be used to predict the energy profiles because relatively large activation energies can be associated with exothermic reactions, as was found for the formation of CH3CF3 (formal addition of trifluoromethyl anion).

  9. Electrochemical oxidation of quaternary ammonium electrolytes : Unexpected side reactions in organic electrochemistry

    NARCIS (Netherlands)

    Nouri Nigjeh, Eslam; de Vries, Marcel; Bruins, Andries P.; Bischoff, Rainer; Permentier, Hjalmar P.

    Quaternary ammonium salts are among the most widely used electrolytes in organic electrochemistry, but there is little known about their unwanted side oxidation reactions. We have, therefore, studied the constant potential oxidation products of quaternary ammonium electrolytes using mass

  10. A catalytic wet oxidation process for mixed waste volume reduction/recycling

    International Nuclear Information System (INIS)

    Dhooge, Patrick M.

    1992-01-01

    Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

  11. Effects of oxygen supply on the biodegradation rate in oil hydrocarbons contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Zawierucha, I [Institute of Chemistry and Environment Protection, Jan Dlugosz University of Czestochowa, Waszyngtona 4/8, 42-200 Czestochowa (Poland); Malina, G, E-mail: iwona_zawierucha@o2.pl [Faculty of Hydrogeology and Geology Engineering, Department of Geology, Geophysics and Environment Protection, AGH University of Science and Technology, Mickiewicza 30, 30-059 Cracow (Poland)

    2011-04-01

    Respirometry studies using the 10-chamber Micro-Oxymax respirometer (Columbus, Ohio) were conducted to determine the effect of biostimulation (by diverse ways of O{sub 2} supply) on enhancing biodegradation in soils contaminated with oil hydrocarbons. Soil was collected from a former military airport in Kluczewo, Poland. Oxygen was supplied by means of aerated water, aqueous solutions of H{sub 2}O{sub 2} and KMnO{sub 4}. The biodegradation was evaluated on the basis of O{sub 2} uptake and CO{sub 2} production. The O{sub 2} consumption and CO{sub 2} production rates during hydrocarbons biodegradation were estimated from the slopes of cumulative curve linear regressions. The pertinent intrinsic and enhanced biodegradation rates were calculated on the basis of mass balance equation and O{sub 2} uptake and CO{sub 2} production rates. The biodegradation rates of 5-7 times higher as compared to a control were observed when the aqueous solution of KMnO{sub 4} in concentration of 20 g L{sup -1} was applied. Permanganate is known to readily oxidize alkene carbon - carbon double bonds; so it can be successfully applied in remediation technology for soils contaminated with oil hydrocarbons. While hydrocarbons are not completely mineralized by permanganate oxidation reactions, their structure is altered by polar functional groups providing vast improvements in aqueous solubility and availability for biodegradation. The 3% aqueous solution of H{sub 2}O{sub 2} caused significant improvement of the biodegradation rates as compared to a control (on average about 260%). Aerobic biodegradation of hydrocarbons can benefit from the presence of oxygen released during H{sub 2}O{sub 2} decomposition. Adding of aerated water resulted in an increase of biodegradation rates (about 114 - 229%) as compared to a control. The aerated water can both be the source of oxygen for microorganisms and determine the transport of substrate to bacteria cells.

  12. The effect of interfaces on solid-state reactions between oxides

    International Nuclear Information System (INIS)

    Johnson, M.T.; Carter, C.B.

    1998-01-01

    A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

  13. A study of the accelerated zircaloy-4 oxidation reaction with H2O/H2 mixture gas

    International Nuclear Information System (INIS)

    Kim, Y. S.; Cho, I. J.

    2001-01-01

    A study of the Zircaloy-4 reaction with H 2 O/H 2 mixture gas is carried out by using TGA (Thermo Gravimetric Apparatus) to estimate the hydrogen embrittlement which can possibly cause catastrophic nuclear fuel rod failure. Reaction rates are measured as a function of H 2 /H 2 O. In the experiments reaction temperature is set at 500 .deg. C and total pressure of the mixture gas is maintained at 1 atm. Experimental results reveal that hydriding and oxidation reaction are competing. In early stage, hydriding kinetics is faster than oxidation, however, oxidant in H 2 O forms oxide on the surface as steam environment is maintained, thus, this growing oxide begins to protect the zirconium base metal against hydrogen permeation. In this second stage, the total kinetic rate follows enhanced oxidation kinetics. In the final stage, it is observed that the oxide is broken down and massive hydriding takes place through the mechanical defects in the oxide, whose kinetics is similar to pure hydriding kinetics. These results are confirmed by SEM and EDX analysis along with hydrogen concentration measurements

  14. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 2

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Arakawa, Kazuo; Sugiura, Toshio.

    1978-01-01

    The ion-molecule reactions in the binary mixture of ethylene oxide and trioxane have been studied with use of a modified time-of-flight mass spectrometer. As cross-reaction product ions, C 3 H 5 O 2 + , C 3 H 6 O 2 +sup(, and C**3**H**7**O**2**)+sup( were observed under the conditions of long delay times and elevated pressure. It was found that these ions are formed by the dissociation of unstable intermediate-complex resulting from the reaction of ethylene oxide molecular ion with trioxane. It was proposed that the complex is of cyclic structure in which positive charge is delocalized. From the consideration of isotopic distribution of the product ions in ethylene-d**4** oxide-trioxane mixtures, the skeletal structures of the product ions were investigated. The rate constants of the formation reactions of C**3**H**5**O**2**)+sup(, C**3**H**6**O**2**)+sup(, and C**3**H**7**O**2**)+sup( in ethylene oxide-trioxane mixtures were found to be 2.20 x 10)-10sup(, 2.61 x 10)-10sup(, and 1.74 x 10)-10sup( cm)3sup( molecule)-1sup(s)-1 , respectively. (auth.)

  15. One-electron oxidation reactions of purine and pyrimidine bases in cellular DNA.

    Science.gov (United States)

    Cadet, Jean; Wagner, J Richard; Shafirovich, Vladimir; Geacintov, Nicholas E

    2014-06-01

    The aim of this survey is to critically review the available information on one-electron oxidation reactions of nucleobases in cellular DNA with emphasis on damage induced through the transient generation of purine and pyrimidine radical cations. Since the indirect effect of ionizing radiation mediated by hydroxyl radical is predominant in cells, efforts have been made to selectively ionize bases using suitable one-electron oxidants that consist among others of high intensity UVC laser pulses. Thus, the main oxidation product in cellular DNA was found to be 8-oxo-7,8-dihydroguanine as a result of direct bi-photonic ionization of guanine bases and indirect formation of guanine radical cations through hole transfer reactions from other base radical cations. The formation of 8-oxo-7,8-dihydroguanine and other purine and pyrimidine degradation products was rationalized in terms of the initial generation of related radical cations followed by either hydration or deprotonation reactions in agreement with mechanistic pathways inferred from detailed mechanistic studies. The guanine radical cation has been shown to be implicated in three other nucleophilic additions that give rise to DNA-protein and DNA-DNA cross-links in model systems. Evidence was recently provided for the occurrence of these three reactions in cellular DNA. There is growing evidence that one-electron oxidation reactions of nucleobases whose mechanisms have been characterized in model studies involving aqueous solutions take place in a similar way in cells. It may also be pointed out that the above cross-linked lesions are only produced from the guanine radical cation and may be considered as diagnostic products of the direct effect of ionizing radiation.

  16. Imaging fluid/solid interactions in hydrocarbon reservoir rocks.

    Science.gov (United States)

    Uwins, P J; Baker, J C; Mackinnon, I D

    1993-08-01

    The environmental scanning electron microscope (ESEM) has been used to image liquid hydrocarbons in sandstones and oil shales. Additionally, the fluid sensitivity of selected clay minerals in hydrocarbon reservoirs was assessed via three case studies: HCl acid sensitivity of authigenic chlorite in sandstone reservoirs, freshwater sensitivity of authigenic illite/smectite in sandstone reservoirs, and bleach sensitivity of a volcanic reservoir containing abundant secondary chlorite/corrensite. The results showed the suitability of using ESEM for imaging liquid hydrocarbon films in hydrocarbon reservoirs and the importance of simulating in situ fluid-rock interactions for hydrocarbon production programmes. In each case, results of the ESEM studies greatly enhanced prediction of reservoir/borehole reactions and, in some cases, contradicted conventional wisdom regarding the outcome of potential engineering solutions.

  17. Recovering hydrocarbons with surfactants from lignin

    Energy Technology Data Exchange (ETDEWEB)

    Naae, D.G.; Whittington, L.E.; Ledoux, W.A.; Debons, F.E.

    1988-11-29

    This patent describes a method of recovering hydrocarbons from an underground hydrocarbon formation penetrated by at least one injection well and at least one production well, which comprises: injecting into the formation through an injection well a surfactant slug comprising about 0.1% to about 10% by weight of surfactants produced from lignin, the surfactants produced by placing lignin in contact with water, converting the lignin into low molecular weight lignin phenols by reducing the lignin in the presence of a reducing agent of carbon monoxide or hydrogen creating a reduction reaction mixture comprising oil soluble lignin phenols, the reduction occurring at a temperature greater than about 200/sup 0/C and a pressure greater than about 100 psi, recovering the oil soluble lignin phenols from the reduction mixture, and converting the lignin phenols into lignin surfactants by a reaction selected from the group consisting of alkoxylation, sulfonation, sulfation, aklylation, sulfomethylation, and alkoxysulfation; injecting into the formation through the injection well a drive fluid to push the surfactant slug towards a production well; and recovering hydrocarbons at the production well.

  18. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  19. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  20. Microbial Hydrocarbon and ToxicPollutant Degradation Method

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, Dietrich [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Janabi, Mustafa [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); O' Neil, James [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Budinger, Thomas [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2011-08-16

    The goal of this project is to determine optimum conditions for bacterial oxidation of hydrocarbons and long-chain alkanes that are representative of petroleum contamination of the environment. Polycyclic Aromatic Hydrocarbons (PAHs) are of concern because of their toxicity, low volatility, and resistance to microbial degradation, especially under anaerobic conditions. The uniqueness of our approach is to use carbon-11 in lieu of the traditional use of carbon-14.

  1. Chemiluminescence from the reaction of Ba 3D with nitric oxide

    International Nuclear Information System (INIS)

    Johnson, S.A.; Solarz, R.W.; Dubrin, J.W.; Brotzmann, R.

    1977-01-01

    The reaction of laser excited Ba*( 3 D) states with nitric oxide is presented. BaO product is not detected, although the channel is thermodynamically open, and instead chemiluminescence is observed. Experiments which suggest that radiative recombination, Ba + NO → BaNO* → BaNO, is the observed reaction channel will also be presented

  2. Catalytic cracking of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1940-09-12

    A process is described for the vapor phase catalytic cracking of hydrocarbon oils boiling substantially in the gas oil range. The reaction takes place in the presence of a solid catalyst between 700 to 900/sup 0/F under pressure between atmospheric and 400 psi. A gas containing between 20 and 90 mol % of free hydrogen is used. The reaction is allowed to proceed until consumption of the free begins. The reaction is discontinued at that point and the catalyst is regenerated for further use.

  3. Hydrodeoxygenation of oxidized distilled bio-oil for the production of gasoline fuel type

    International Nuclear Information System (INIS)

    Luo, Yan; Guda, Vamshi Krishna; Hassan, El Barbary; Steele, Philip H.; Mitchell, Brian; Yu, Fei

    2016-01-01

    Highlights: • Oxidation had more influence on the yield of total hydrocarbons than distillation. • The highest total hydrocarbon yield was obtained from oxidized distilled bio-oil. • The 2nd-stage hydrocarbons were in the range of gasoline fuel boiling points. • The main products for upgrading of oxidized bio-oil were aliphatic hydrocarbons. • The main products for upgrading of non-oxidized bio-oil were aromatic hydrocarbons. - Abstract: Distilled and oxidized distilled bio-oils were subjected to 1st-stage mild hydrodeoxygenation and 2nd-stage full hydrodeoxygenation using nickel/silica–alumina catalyst as a means to enhance hydrocarbon yield. Raw bio-oil was treated for hydrodeoxygenation as a control to which to compare study treatments. Following two-stage hydrodeoxygenation, four types of hydrocarbons were mainly comprised of gasoline and had water contents, oxygen contents and total acid numbers of nearly zero and higher heating values of 44–45 MJ/kg. Total hydrocarbon yields for raw bio-oil, oxidized raw bio-oil, distilled bio-oil and oxidized distilled bio-oil were 11.6, 16.2, 12.9 and 20.5 wt.%, respectively. The results indicated that oxidation had the most influence on increasing the yield of gasoline fuel type followed by distillation. Gas chromatography/mass spectrometry characterization showed that 66.0–76.6% of aliphatic hydrocarbons and 19.5–31.6% of aromatic hydrocarbons were the main products for oxidized bio-oils while 35.5–38.7% of aliphatic hydrocarbons and 58.2–63.1% of aromatic hydrocarbons were the main products for non-oxidized bio-oils. Both aliphatic and aromatic hydrocarbons are important components for liquid transportation fuels and chemical products.

  4. The Role of Post Flame Oxidation on the UHC Emission for Combustion of Natural Gas and Hydrogen Containing fuels

    DEFF Research Database (Denmark)

    Jensen, Torben Kvist; Schramm, Jesper

    2003-01-01

    In-cylinder post flame oxidation of unburned hydro-carbons from crevices in a lean burn spark ignition engine has been examined for natural gas and mixtures of natural gas and a hydrogen containing producer gas. For this purpose a model was developed to describe the mixing of cold unburned...... reactants from crevices and hot burned bulk gas and to describe the oxidation of the unburned fuel. The post oxidation was described by a single step chemical reaction mechanism instead of detailed chemical kinetics in order to reduce the calculation time. However, the exploited Arrhenius expressions used...... to describe the chemical reactions were deduced from a detailed reaction mechanism. Different detailed reaction mechanisms were compared with results from combustion reactor experiments. Experiments and simulations were compared at different pressures and excesses of air similar to the conditions present...

  5. Nonthermal plasma reactors for the production of light hydrocarbon olefins from heavy oil

    Directory of Open Access Journals (Sweden)

    G. Prieto

    2003-03-01

    Full Text Available During the last decade, nonthermal plasma technology was applied in many different fields, focusing attention on the destruction of harmful compounds in the air. This paper deals with nonthermal plasma reactors for the conversion of heavy oil into light hydrocarbon olefins, to be employed as gasoline components or to be added in small amounts for the catalytic reduction of nitrogen oxide compounds in the treatment of exhaust gas at power plants. For the process, the plate-plate nonthermal plasma reactor driven by AC high voltage was selected. The reactor was modeled as a function of parameter characteristics, using the methodology provided by the statistical experimental design. The parameters studied were gap distance between electrodes, carrier gas flow and applied power. Results indicate that the reactions occurring in the process of heavy oil conversion have an important selective behavior. The products obtained were C1-C4 hydrocarbons with ethylene as the main compound. Operating the parameters of the reactor within the established operative window of the system and close to the optimum conditions, efficiencies as high as 70 (mul/joule were obtained. These values validate the process as an in-situ method to produce light olefins for the treatment of nitrogen oxides in the exhaust gas from diesel engines.

  6. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    Science.gov (United States)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  7. Pulse radiolysis study on oxidation reactions of gallic acid

    International Nuclear Information System (INIS)

    Dwibedy, P.; Dey, G.R.; Naik, D.B.; Kishore, Kamal

    1998-01-01

    Reactions of OH . /O - and other oxidising radicals viz. N 3 . , Br 2 .- , Cl 2 .- with gallic acid (GA) have been studied at various pHs. At pH 6.8, OH . radicals react with GA giving an adduct which in turn reacts with the parent GA to give a dimeric species. At pH 9.7, the initial OH adduct formed is able to oxidize GA to give a semi-oxidised species. At pH 12 and ∼ 13.6, OH . /O .- radicals directly bring about oxidation of GA. (author)

  8. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  9. CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes

    Science.gov (United States)

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was fo...

  10. Thermodynamic analysis of combined Solid Oxide Electrolyzer and Fischer–Tropsch processes

    International Nuclear Information System (INIS)

    Stempien, Jan Pawel; Ni, Meng; Sun, Qiang; Chan, Siew Hwa

    2015-01-01

    In this paper a thermodynamic analysis and simple optimization of a combined Solid Oxide Electrolyzer Cell and Fisher–Tropsch Synthesis processes for sustainable hydrocarbons fuel production is reported. Comprehensive models are employed to describe effects of temperature, pressure, reactant composition and molar flux and flow on the system efficiency and final production distribution. The electrolyzer model was developed in-house and validated with experimental data of a typical Solid Oxide Electrolyzer. The Fischer–Tropsch Synthesis model employed lumped kinetics of syngas utilization, which includes inhibiting effect of water content and kinetics of Water–Gas Shift reaction. Product distribution model incorporated olefin re-adsorption and varying physisorption and solubility of hydrocarbons with their carbon number. The results were compared with those reported by Becker et al. with simplified analysis of such process. In the present study an opposite effect of operation at elevated pressure was observed. Proposed optimized system achieved overall efficiency of 66.67% and almost equal spread of light- (31%wt), mid-(36%wt) and heavy-hydrocarbons (33%wt). Paraffins contributed the majority of the yield. - Highlights: • Analysis of Solid Oxide Electrolyzer combined with Fisher Tropsch process. • Efficiency of converting water and carbon dioxide into synthetic fuels above 66%. • Effects of process temperature, pressure, gas flux and compositions were analyzed

  11. Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

    The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

  12. A coupled mechanical-chemical model for reflecting the influence of stress on oxidation reactions in thermal barrier coating

    Science.gov (United States)

    Chen, Lin; Yueming, Li

    2018-06-01

    In this paper, a coupled mechanical-chemical model is established based on the thermodynamic framework, in which the contribution of chemical expansion to free energy is introduced. The stress-dependent chemical potential equilibrium at the gas-solid interface and the stress gradient-dependent diffusion equation as well as a so-called generalized force which is conjugate to the oxidation rate are derived from the proposed model, which could reflect the influence of stresses on the oxidation reaction. Based on the proposed coupled mechanical-chemical model, a user element subroutine is developed in ABAQUS. The numerical simulation of the high temperature oxidation in the thermal barrier coating is carried out to verify the accuracy of the proposed model, and then the influence of stresses on the oxidation reaction is investigated. In thermally grown oxide, the considerable stresses would be induced by permanent volumetric swelling during the oxidation. The stresses play an important role in the chemical potential equilibrium at the gas-solid interface and strongly affect the oxidation reaction. The gradient of the stresses, however, only occurs in the extremely thin oxidation front layer, which plays a very limited role in the oxidation reaction. The generalized force could be divided into the stress-dependent and the stress-independent parts. Comparing with the stress-independent part, the stress-dependent part is smaller, which has little influence on oxidation reaction.

  13. First principles modeling of hydrocarbons conversion in non-equilibrium plasma

    Energy Technology Data Exchange (ETDEWEB)

    Deminsky, M.A.; Strelkova, M.I.; Durov, S.G.; Jivotov, V.K.; Rusanov, V.D.; Potapkin, B.V. [Russian Research Centre Kurchatov Inst., Moscow (Russian Federation)

    2001-07-01

    Theoretical justification of catalytic activity of non-equilibrium plasma in hydrocarbons conversion process is presented in this paper. The detailed model of highest hydrocarbons conversion includes the gas-phase reactions, chemistry of the growth of polycyclic aromatic hydrocarbons (PAHs), precursor of soot particles formation, neutral, charged clusters and soot particle formation, ion-molecular gas-phase and heterogeneous chemistry. The results of theoretical analysis are compared with experimental results. (authors)

  14. Oxidation of Hydrocarbons on the Surface of Tin Dioxide Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Izabela Polowczyk

    2011-04-01

    Full Text Available The paper presents the results of our investigation on the effect of the molecular structure of organic vapors on the characteristics of resistive chemical gas sensors. The sensors were based on tin dioxide and prepared by means of thick film technology. The electrical and catalytic examinations showed that the abstraction of two hydrogen atoms from the organic molecule and formation of a water in result of reaction with a chemisorbed oxygen ion, determine the rate of oxidation reactions, and thus the sensor performance. The rate of the process depends on the order of carbon atoms and Lewis acidity of the molecule. Therefore, any modification of the surface centers of a sensor material, modifies not only the sensor sensitivity, but also its selectivity.

  15. GC of catalytic reactions products involved in the promising fuel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Zheivot, V.; Sazonova, N. [Russian Academy of Sciences, Novosibirsk (Russian Federation). Boreskov Inst. of Catalysis

    2012-09-15

    Catalytic reactions involved in the synthesis of the promising kinds of novel fuel and products formed in these reactions were systematized according to the resulting fuel type. Generalization of the retention of the substances comprising these products is presented. Chromatograms exhibiting their separation on chromatographic materials with the surface of different chemical properties are summarized. We propose procedures for gas-chromatographic analysis of the catalytic reactions products formed in the synthesis of hydrogen, methanol, dimethyl ether and hydrocarbons as a new generation of fuel alternative to petroleum and coal. For partial oxidation of methane into synthesis gas, on-line determination of the components obtained in the reaction was carried out by gas chromatography and gas analyzer based on different physicochemical methods (IR spectroscopy and electrochemical methods). Similarity of the results obtained using these methods is demonstrated. (orig.)

  16. Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

    Science.gov (United States)

    Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

    2003-05-01

    Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

  17. Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

    2008-12-05

    The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

  18. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

  19. Thermodynamic analysis of synthetic hydrocarbon fuel production in pressurized solid oxide electrolysis cells

    DEFF Research Database (Denmark)

    Sun, Xiufu; Chen, Ming; Jensen, Søren Højgaard

    2012-01-01

    A promising way to store wind and solar electricity is by electrolysis of H2O and CO2 using solid oxide electrolysis cells (SOECs) to produce synthetic hydrocarbon fuels that can be used in existing fuel infrastructure. Pressurized operation decreases the cell internal resistance and enables...... improved system efficiency, potentially lowering the fuel production cost significantly. In this paper, we present a thermodynamic analysis of synthetic methane and dimethyl ether (DME) production using pressurized SOECs, in order to determine feasible operating conditions for producing the desired......, and outlet gas composition. For methane production, low temperature and high pressure operation could improve the system efficiency, but might lead to a higher capital cost. For DME production, high pressure SOEC operation necessitates higher operating temperature in order to avoid carbon formation at higher...

  20. Analysis of reaction products formed in the gas phase reaction of E,E-2,4-hexadienal with atmospheric oxidants: Reaction mechanisms and atmospheric implications

    Science.gov (United States)

    Colmenar, I.; Martin, P.; Cabañas, B.; Salgado, S.; Martinez, E.

    2018-03-01

    An analysis of reaction products for the reaction of E,E-2,4-hexadienal with chlorine atoms (Cl) and OH and NO3 radicals has been carried out at the first time with the aim of obtaining a better understanding of the tropospheric reactivity of α,β-unsaturated carbonyl compounds. Fourier Transform Infrared (FTIR) spectroscopy and Gas Chromatography-Mass Spectrometry with a Time of Flight detector (GC-TOFMS) were used to carry out the qualitative and/or quantitative analyses. Reaction products in gas and particulate phase were observed from the reactions of E,E-2,4- hexadienal with all oxidants. E/Z-Butenedial and maleic anhydride were the main products identified in gas phase. E-butenedial calculated molar yield ranging from 4 to 10%. A significant amount of multifunctional compounds (chloro and hydroxy carbonyls) was identified. These compounds could be formed in particulate phase explaining the ∼90% of unaccounted carbon in gas phase. The reaction with Cl atoms in the presence of NOx with a long reaction time gave Peroxy Acetyl Nitrate (PAN) as an additional product, which is known for being an important specie in the generation of the photochemical smog. Nitrated compounds were the major organic products from the reaction with the NO3 radical. Based on the identified products, the reaction mechanisms have been proposed. In these mechanisms a double bond addition of the atmospheric oxidant at C4/C5 of E,E-2,4-hexadienal is the first step for tropospheric degradation.

  1. One-step hydroprocessing of fatty acids into renewable aromatic hydrocarbons over Ni/HZSM-5: insights into the major reaction pathways.

    Science.gov (United States)

    Xing, Shiyou; Lv, Pengmei; Wang, Jiayan; Fu, Junying; Fan, Pei; Yang, Lingmei; Yang, Gaixiu; Yuan, Zhenhong; Chen, Yong

    2017-01-25

    For high caloricity and stability in bio-aviation fuels, a certain content of aromatic hydrocarbons (AHCs, 8-25 wt%) is crucial. Fatty acids, obtained from waste or inedible oils, are a renewable and economic feedstock for AHC production. Considerable amounts of AHCs, up to 64.61 wt%, were produced through the one-step hydroprocessing of fatty acids over Ni/HZSM-5 catalysts. Hydrogenation, hydrocracking, and aromatization constituted the principal AHC formation processes. At a lower temperature, fatty acids were first hydrosaturated and then hydrodeoxygenated at metal sites to form long-chain hydrocarbons. Alternatively, the unsaturated fatty acids could be directly deoxygenated at acid sites without first being saturated. The long-chain hydrocarbons were cracked into gases such as ethane, propane, and C 6 -C 8 olefins over the catalysts' Brønsted acid sites; these underwent Diels-Alder reactions on the catalysts' Lewis acid sites to form AHCs. C 6 -C 8 olefins were determined as critical intermediates for AHC formation. As the Ni content in the catalyst increased, the Brønsted-acid site density was reduced due to coverage by the metal nanoparticles. Good performance was achieved with a loading of 10 wt% Ni, where the Ni nanoparticles exhibited a polyhedral morphology which exposed more active sites for aromatization.

  2. A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction.

    Science.gov (United States)

    Lee, Lanlee; Kang, Byungwuk; Han, Suyoung; Kim, Hee-Eun; Lee, Moo Dong; Bang, Jin Ho

    2018-05-27

    A thermal reaction route that induces grain fracture instead of grain growth is devised and developed as a top-down approach to prepare nanostructured oxides from bulk solids. This novel synthesis approach, referred to as the sequential oxygen-nitrogen exchange (SONE) reaction, exploits the reversible anion exchange between oxygen and nitrogen in oxides that is driven by a simple two-step thermal treatment in ammonia and air. Internal stress developed by significant structural rearrangement via the formation of (oxy)nitride and the creation of oxygen vacancies and their subsequent combination into nanopores transforms bulk solid oxides into nanostructured oxides. The SONE reaction can be applicable to most transition metal oxides, and when utilized in a lithium-ion battery, the produced nanostructured materials are superior to their bulk counterparts and even comparable to those produced by conventional bottom-up approaches. Given its simplicity and scalability, this synthesis method could open a new avenue to the development of high-performance nanostructured electrode materials that can meet the industrial demand of cost-effectiveness for mass production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Catalysis by mixed oxide perovskites. II. The hydrogenolysis of C/sub 3/-C/sub 5/ hydrocarbons on LaCoO/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Ichimura, K; Inoue, Y; Yasumori, I

    1981-06-01

    The catalytic hydrogenolysis of C/sub 3/ to C/sub 5/ alkanes on LaCoO/sub 3/ perovskite oxide was found to show a highly selective formation of methane in the temperature range of 350 to 620 K. The reaction order with respect to the hydrocarbon pressure was unity in every hydrogenolysis, whereas, the hydrogen order increased from zero for propane to 1.0 for butane and isobutane and to 2.0 for pentane, isopentane, and neopentane. The activation energies of the reactions ranged from 120 for propane to 32 kJ mol/sup -1/ for butane. The reaction of propane or butane with D/sub 2/ on LaCoO/sub 3/ provided large fractions of methane (D/sub 3/) and (D/sub 4/), but a negligible amount of deuterium-exchanged alkanes. An equilibrium among the gaseous H/sub 2/, HD and D/sub 2/ was reached. These hydrogenolyses are described by a mechanism involving the almost concurrent rupture of all the carbon-carbon bonds in the alkanes by the attack of adsorbed hydrogen atoms, and were proposed to be catalyzed by a synergetic effect; the CO/sup 3 +/ ion is effective in breaking the C-C bond, whereas the La/sup 3 +/ and O/sup 2 -/ ions serve to supply hydrogen atoms to the decomposed species. The reaction of propene or butenes with hydrogen produced the corresponding alkanes and methane. The kinetic analyses showed that the fractions of methane produced consecutively via the alkanes amounted to 16% for propene and to more than 93% for butenes. The observed pressure dependence and deuterium distributions in the alkene hydrogenation were interpreted in terms of the associative mechanism. The correlation between the structures of the reactant molecules and of the active sites present on LaCoO/sub 3/ was briefly discussed.

  4. The effect of supercritical isobutane regeneration on the nature of hydrocarbons deposited on a USY zeolite catalyst utilized for isobutane/butene alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; Lucia M. Petkovic

    2004-11-01

    The chemical nature of hydrocarbons remaining on an ultrastable Y-zeolite (USY) utilized for liquid phase isobutane/butene alkylation reaction at 333 K and 1.1x107 Pa before and after supercritical isobutane regeneration (SFR) at 453 K and 1.1x107 Pa are presented. Catalyst samples were deactivated to different levels by running the alkylation reaction for different times on stream (TOS) and regenerated under flowing supercritical isobutane for 60 min. Nitrogen physisorption, temperature-programmed oxidation (TPO), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and ultraviolet-visible (UV-Vis) spectroscopy measurements suggested that the SFR process was effective in recovering catalyst surface area and micropore volume and that most coke precursors were removed from samples regenerated after short TOS, when the level of activity for trimethylpentanes (TMP) production was high. Samples that were allowed to react for longer TOS contained unsaturated hydrocarbons that, instead of being extracted by the supercritical fluid, dehydrogenated during the SFR process to produce more condensed species.

  5. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

    International Nuclear Information System (INIS)

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-01-01

    The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

  6. Laboratory evaluation of PAH oxidation by magnesium peroxides and iron oxides mixtures as reactive material for groundwater remediation

    International Nuclear Information System (INIS)

    Valderrama, C.; Gamisans, X.; Cortina, J.L.; Farran, A.; Marti, V.

    2005-01-01

    contaminant(s) of concern; 2) the total oxidant requirements, pH dependence and relative reaction rate, and 3) the reaction by-products formed. The main goal of this work the evaluation of mixtures of magnesium peroxide and iron oxides as reactive materials for Poly-aromatic Hydrocarbons (PAH) degradation reagents in permeable reactive barriers or zones. One goal of this study is to examine and determine the release rate of hydrogen peroxide from magnesium peroxide by means of laboratory experiments. The magnesium peroxide from two different sources (i.e. Regenesis and Solvay) will be compared. Another objective is to study how a catalyst such as iron speeds up the degradation of PAHs. Not only the release rate will be studied, but also the dissolution process of magnesium peroxide. The experiments mentioned above will be carried out in both batch and continuous reactors. The results of this study showed that the magnesium peroxide from Solvay can release more hydrogen peroxide than the magnesium peroxide from Regenesis. The oxidation factors for the two preparations are quite similar, even though the release of hydrogen peroxide differs greatly. Another point, which ought to be considered, is the minor effect of iron oxides in the degradation of PAHs. The dissolution process of magnesium peroxide is a complex process with magnesium hydroxide as the main reaction by product. So, magnesium peroxides can be used as a hydrogen peroxide releasing compound. Further studies on the removal mechanisms should be performed to identify the oxidation products as well as the sorption properties of magnesium hydroxide. The heterogeneous oxidation of a family of poly-aromatic hydrocarbons (anthracene, pyrene, fluorene and naphthalene) proceeds with a highly efficiency ratio and following a first order kinetic

  7. Microbial Fe(II) oxidation at circumneutral pH: Reaction kinetics, mineral products, and distribution of neutrophilic iron oxidizers in wetland soils

    NARCIS (Netherlands)

    Vollrath, S.

    2012-01-01

    Multiple studies have shown that neutrophilic Fe(II) oxidizers can conserve energy from Fe(II) oxidation, however, it is still unclear how they can compete against the fast abiotic reaction at neutral pH, or to which extent these bacteria increase the overall Fe(II) oxidation rate. Similar to

  8. Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

    Science.gov (United States)

    Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

    2013-07-07

    A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

  9. Study of reactions between uranium-plutonium mixed oxide and uranium nitride and between uranium oxide and uranium nitride; Etude des reactions entre l`oxyde mixte d`uranium-plutonium et le nitrure d`uranium et entre l`oxyde d`uranium et le nitrure d`uranium

    Energy Technology Data Exchange (ETDEWEB)

    Lecraz, C

    1993-06-11

    A new type of combustible elements which is a mixture of uranium nitride and uranium-plutonium oxide could be used for Quick Neutrons Reactors. Three different studies have been made on the one hand on the reactions between uranium nitride (UN) and uranium-plutonium mixed oxide (U,Pu)O{sub 2}, on the other hand on these between UN and uranium oxide UO{sub 2}. They show a sizeable reaction between nitride and oxide for the studied temperatures range (1573 K to 1973 K). This reaction forms a oxynitride compound, MO{sub x} N{sub y} with M=U or M=(U,Pu), whose crystalline structure is similar to oxide`s. Solubility of nitride in both oxides is studied, as the reaction kinetics. (TEC). 32 refs., 48 figs., 22 tabs.

  10. Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

    International Nuclear Information System (INIS)

    Montemagno, C.D.; Peters, R.W.; Tyree, A.

    1991-01-01

    Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

  11. Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Montemagno, C. D. [Argonne National Laboratory, Argonne, IL (United States); Peters, R. W.; Tyree, A.

    1991-07-01

    Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

  12. IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

    Science.gov (United States)

    de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

    2015-10-28

    The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-06

    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.

  15. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    situation. Growing families of synthetic iron complexes that resemble active sites of metalloenzymes produce metal-based intermediates (rather than hydroxyl radicals) in reactions with oxygen donors. These complexes are very promising for selective oxygen and peroxide activation. In order to understand the mechanisms of metal-based small molecule activation, kinetically competent metal-oxygen intermediates must be identified. One of the grand challenges identified by the Department of Energy workshop "Catalysis for Energy" is understanding mechanisms and dynamics of catalyzed reactions. The research summarized herein focuses on detailed characterization of the formation and reactivity of various iron-peroxo- and iron-oxo intermediates that are involved in catalysis. Rates of rapid reactions were studied at low temperatures by a specialized technique termed cryogenic stopped-flow spectrophotometry. These measurements identified reaction conditions which favor the formation of catalytically competent oxidants. Chemical structures of reactive complexes was determined, and new, efficient catalysts for hydrocarbon oxidation were synthesized. Importantly, these catalysts are selective, they promote oxidation of hydrocarbons at a specific site. The catalysts are also efficient and robust, hundreds of cycles of substrate oxidation occur within minutes at room temperature. Furthermore, they enable utilization of environmentally friendly oxidants, such as hydrogen peroxide, which produces water as the only byproduct. Mechanistic insights uncovered the role of various acid-containing additives in catalytic oxidations. Proton delivery to the active catalytic sites facilitated oxidations, similarly to the catalytic pathways in metal-containing enzymes. Under certain conditions, two metals in one complex can act in concert, modeling the reactivity of a bacterial enzyme which converts methane into methanol. In related studies, a family of nickel complexes that react with carbon dioxide at

  16. Iron(III) porphyrin-catalysed oxidation reactions by m-chloro ...

    Indian Academy of Sciences (India)

    Unknown

    The notable feature in this study is that none of the kinetic traces are expo- nential. A representative plot is given in figure 1 and the quantitative spectrum of TTBP• radical in dichloromethane is given in figure 2 (bold line). In this oxidation reaction under all the conditions, non-exponential kinetic traces were always obser-.

  17. Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

    Science.gov (United States)

    Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

    2018-04-01

    The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

  18. Recycling Carbon Dioxide into Sustainable Hydrocarbon Fuels: Electrolysis of Carbon Dioxide and Water

    Science.gov (United States)

    Graves, Christopher Ronald

    -electrolysis of CO2 and H2O to produce syngas (CO/H2 mixture) is identified as a promising method. High temperature electrolysis makes very efficient use of electricity and heat (near-100% electricity-to-syngas efficiency), provides high reaction rates, and the syngas produced can be catalytically converted to hydrocarbons in well-known fuel synthesis reactors (e.g. Fischer-Tropsch). The experimental studies of high temperature electrolysis are made at different scales -- at the cell level, electrode level, and in materials and microstructure development. The results include cell performance and durability, insight into electrode reaction mechanisms, and new high-performance electrode materials. The experimental studies make extensive use of electrochemical impedance spectroscopy and systematic variation of test conditions to examine the electrochemical phenomena. Variation of the material composition itself within families of related materials was an additional parameter used in the electrode level and materials studies that revealed more information than studying a single material would have. Using full cells, the performance and durability of a solid oxide cell applied for co-electrolysis of CO2 and H2O was investigated. High initial performance was observed but the long-term durability needs to be improved. Based on these results, an analysis of the energy balance and economics of an electrolysis-based synthetic fuel production process, including CO2 air capture and Fischer-Tropsch fuel synthesis, determined that the system can feasibly operate at 70% electricity-to-liquid fuel efficiency (higher heating value basis) and that the price of electricity needed to produce competitive synthetic gasoline (at USD2/gal, or 0.53/L, wholesale) is 2-3 U.S. cents per kWh. For 3/gal (0.78/L) gasoline, 4-5 cents per kWh is needed. Fuel production may already be economical in some regions that have inexpensive renewable electricity, such as Iceland. The dominant costs of the process are the

  19. Oxidative coupling of methane using inorganic membrane reactor

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Y.H.; Moser, W.R.; Dixon, A.G. [Worcester Polytechnic Institute, MA (United States)] [and others

    1995-12-31

    The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

  20. Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene.

    Science.gov (United States)

    Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Chen, Jianmin; Wang, Wenxing

    2014-08-15

    The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72×10(-11) cm(3) molecule(-1) s(-1) at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  2. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-04-26

    With the increasing production of natural gas as a result of the advancement in the technology, methane conversion to more valuable products has become a must. One of the most attractive processes which allow the utilization of the world’s most abundant hydrocarbon is the oxidative coupling. The main advantage of this process is the ability of converting methane into higher paraffins and olefins (primarily C2) in a direct way using a single reactor. Nevertheless, low C2+ yields have prevented the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized in improving the catalysts’ performance. The reaction involves the formation of methyl radicals that undergo gas-phase radical reactions. CH4 activation is believed to be done the surface oxygen species. However, recent studies showed that, in addition to the surface oxygen mediated pathway, an OH radical mediated pathway have a large contribution on the CH4 activation. The experiments of Li/MgO, Sr/La2O3 and NaWO4/SiO2 catalysts revealed variation of behavior in activity and selectivity. In addition, water effect analysis showed that Li/MgO deactivate at the presence of water due to sintering phenomena and the loss of active sites. On the other hand, negative effect on the C2 yield and CH4 conversion rate was observed with Sr/La2O3 with increasing the water partial pressure. Na2WO4/SiO2 showed a positive behavior with water in terms of CH4 conversion and C2 yield. In addition, the increment in CH4 conversion rate was found to be proportional with PO2 ¼ PH2O ½ which is consistent with the formation of OH radicals and the OH-mediated pathway. Experiments of using ring-dye laser, which is used to detect OH in combustion experiments, were tried in order to detect OH radicals in the gas-phase of the catalyst. Nevertheless

  3. Preparing valuable hydrocarbons by hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M

    1930-08-22

    A process is described for the preparation of valuable hydrocarbons by treatment of carbonaceous materials, like coal, tars, minerals oils, and their distillation and conversion products, and for refining of liquid hydrocarbon mixture obtained at raised temperature and under pressure, preferably in the presence of catalysts, by the use of hydrogen-containing gases, purified and obtained by distilling solid combustibles, characterized by the purification of the hydrogen-containing gases being accomplished for the purpose of practically complete removal of the oxygen by heating at ordinary or higher pressure in the presence of a catalyst containing silver and oxides of metals of group VI of the periodic system.

  4. The Nernst equation applied to oxidation-reduction reactions in myoglobin and hemoglobin. Evaluation of the parameters.

    Science.gov (United States)

    Saroff, Harry A

    Analyses of the binding of oxygen to monomers such as myoglobin employ the Mass Action equation. The Mass Action equation, as such, is not directly applicable for the analysis of the binding of oxygen to oligomers such as hemoglobin. When the binding of oxygen to hemoglobin is analyzed, models incorporating extensions of mass action are employed. Oxidation-reduction reactions of the heme group in myoglobin and hemoglobin involve the binding and dissociation of electrons. This reaction is described with the Nernst equation. The Nernst equation is applicable only to a monomeric species even if the number of electrons involved is greater than unity. To analyze the oxidation-reduction reaction in a molecule such as hemoglobin a model is required which incorporates extensions of the Nernst equation. This communication develops models employing the Nernst equation for oxidation-reduction reactions analogous to those employed for hemoglobin in the analysis of the oxygenation (binding of oxygen) reaction.

  5. Sensitizing effects of NOx on CH4 oxidation at high pressure

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund; Rasmussen, Anja Egede; Glarborg, Peter

    2008-01-01

    The CH4/O2/NOx system is investigated in a laboratory-scale high pressure laminar flow reactor with the purpose of elucidating the sensitizing effects of NOx on CH4 oxidation at high pressures and medium temperatures. Experiments are conducted at 100, 50, and 20 bar, 600-900 K, and stoichiometric...... ratios ranging from highly reducing to oxidizing conditions. The experimental results are interpreted in terms of a detailed kinetic model drawn from previous work of the authors, including an updated reaction subset for the direct interactions of NOx and C1-2 hydrocarbon species relevant...

  6. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  7. GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

    Science.gov (United States)

    Xu, X.; Williams, C.; Plass-Dülmer, H.; Berresheim, H.; Salisbury, G.; Lange, L.; Lelieveld, J.

    2003-09-01

    During the Mediterranean Intensive Oxidant Study (MINOS) campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC) at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene) to 43±36 pptv (toluene). The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH) and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and related data

  8. The family of berberine bridge enzyme-like enzymes: A treasure-trove of oxidative reactions.

    Science.gov (United States)

    Daniel, Bastian; Konrad, Barbara; Toplak, Marina; Lahham, Majd; Messenlehner, Julia; Winkler, Andreas; Macheroux, Peter

    2017-10-15

    Biological oxidations form the basis of life on earth by utilizing organic compounds as electron donors to drive the generation of metabolic energy carriers, such as ATP. Oxidative reactions are also important for the biosynthesis of complex compounds, i.e. natural products such as alkaloids that provide vital benefits for organisms in all kingdoms of life. The vitamin B 2 -derived cofactors flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) enable an astonishingly diverse array of oxidative reactions that is based on the versatility of the redox-active isoalloxazine ring. The family of FAD-linked oxidases can be divided into subgroups depending on specific sequence features in an otherwise very similar structural context. The sub-family of berberine bridge enzyme (BBE)-like enzymes has recently attracted a lot of attention due to the challenging chemistry catalyzed by its members and the unique and unusual bi-covalent attachment of the FAD cofactor. This family is the focus of the present review highlighting recent advancements into the structural and functional aspects of members from bacteria, fungi and plants. In view of the unprecedented reaction catalyzed by the family's namesake, BBE from the California poppy, recent studies have provided further insights into nature's treasure chest of oxidative reactions. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  9. Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid.

    Science.gov (United States)

    Lederer, Madeline R; Staniec, Allison R; Coates Fuentes, Zoe L; Van Ry, Daryl A; Hinrichs, Ryan Z

    2016-12-08

    Biogenic volatile organic compounds (BVOCs), including the monoterpene limonene, are a major source of secondary organic aerosol (SOA). While gas-phase oxidation initiates the dominant pathway for BVOC conversion to SOA, recent studies have demonstrated that biogenic hydrocarbons can also directly react with acidic droplets. To investigate whether mineral dust may facilitate similar reactive uptake of biogenic hydrocarbons, we studied the heterogeneous reaction of limonene with mineral substrates using condensed-phase infrared spectroscopy and identified the formation of irreversibly adsorbed organic products. For kaolinite, Arizona Test Dust, and silica at 30% relative humidity, GC-MS identified limonene-1,2-diol as the dominant product with total organic surface concentrations on the order of (3-5) × 10 18 molecules m -2 . Experiments with 18 O-labeled water support a mechanism initiated by oxidation of limonene by surface redox sites forming limonene oxide followed by water addition to the epoxide to form limonenediol. Limonene uptake on α-alumina, γ-alumina, and montmorillonite formed additional products in high yield, including carveol, carvone, limonene oxide, and α-terpineol. To model tropospheric processing of mineral aerosol, we also exposed each mineral substrate to gaseous nitric acid prior to limonene uptake and identified similar surface adsorbed products that were formed at rates 2 to 5 times faster than without nitrate coatings. The initial rate of reaction was linearly dependent on gaseous limonene concentration between 5 × 10 12 and 5 × 10 14 molecules cm -3 (0.22-20.5 ppm) consistent with an Eley-Rideal-type mechanism in which gaseous limonene reacts directly with reactive surface sites. Increasing relative humidity decreased the amount of surface adsorbed products indicating competitive adsorption of surface adsorbed water. Using a laminar flow tube reactor we measured the uptake coefficient for limonene on kaolinite at 25% RH to range from

  10. Methods for natural gas and heavy hydrocarbon co-conversion

    Science.gov (United States)

    Kong, Peter C [Idaho Falls, ID; Nelson, Lee O [Idaho Falls, ID; Detering, Brent A [Idaho Falls, ID

    2009-02-24

    A reactor for reactive co-conversion of heavy hydrocarbons and hydrocarbon gases and includes a dielectric barrier discharge plasma cell having a pair of electrodes separated by a dielectric material and passageway therebetween. An inlet is provided for feeding heavy hydrocarbons and other reactive materials to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a variety of light sources for providing ultraviolet light within the discharge plasma cell. Methods for upgrading heavy hydrocarbons are also disclosed.

  11. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

    International Nuclear Information System (INIS)

    Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

    2013-01-01

    A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

  12. Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

    Science.gov (United States)

    Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

    2018-03-06

    To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

  13. Catalytic cracking of vegetable oil with metal oxides for biofuel production

    International Nuclear Information System (INIS)

    Yigezu, Zerihun Demrew; Muthukumar, Karuppan

    2014-01-01

    Highlights: • Biofuel was synthesized from vegetable oil by catalytic cracking. • Performance of six different metal catalysts was studied. • Influence of temperature and reaction time on the process was evaluated. • Methyl and ethyl esters are the major components of the biofuel synthesized. - Abstract: This study presents the utilization of metal oxides for the biofuel production from vegetable oil. The physical and chemical properties of the diesel-like products obtained, and the influence of reaction variables on the product distribution were investigated. Six different metal oxides (Co 3 O 4 , KOH, MoO 3 , NiO, V 2 O 5 , and ZnO) were employed as catalysts and the results indicated that the metal oxides are suitable for catalyzing the conversion of oil into organic liquid products (OLPs). The maximum conversion (87.6%) was obtained with V 2 O 5 at 320 °C in 40 min whereas a minimum conversion (55.1%) was obtained with MoO 3 at 390 °C in 30 min. The physical characteristics of the product obtained (density, specific gravity, higher heat value, flash point and kinematic viscosity), were in line with ASTM D6751 (B100) standards. The hydrocarbons majorly present in the product were found to be methyl and ethyl esters. Furthermore, OLPs obtained were distilled and separated into four components. The amount of light hydrocarbons, gasoline, kerosene and heavy oil like components obtained were 18.73%, 33.62%, 24.91% and 90.93%, respectively

  14. Insights into the superhydrophobicity of metallic surfaces prepared by electrodeposition involving spontaneous adsorption of airborne hydrocarbons

    International Nuclear Information System (INIS)

    Liu, Peng; Cao, Ling; Zhao, Wei; Xia, Yue; Huang, Wei; Li, Zelin

    2015-01-01

    Graphical abstract: - Highlights: • Several superhydrophobic metallic surfaces were fabricated by fast electrodeposition. • Both micro/nanostructures and adsorption of airborne hydrocarbons make contributions. • XPS analyses confirm presence of airborne hydrocarbons on these metallic surfaces. • The adsorption of airborne hydrocarbons on the clean metal Au surface was very quick. • UV-O 3 treatment oxidized the hydrocarbons to hydrophilic oxygen-containing organics. - Abstract: Electrochemical fabrication of micro/nanostructured metallic surfaces with superhydrophobicity has recently aroused great attention. However, the origin still remains unclear why smooth hydrophilic metal surfaces become superhydrophobic by making micro/nanostructures without additional surface modifications. In this work, several superhydrophobic micro/nanostructured metal surfaces were prepared by a facile one-step electrodeposition process, including non-noble and noble metals such as copper, nickel, cadmium, zinc, gold, and palladium with (e.g. Cu) or without (e.g. Au) surface oxide films. We demonstrated by SEM and XPS that both hierarchical micro/nanostructures and spontaneous adsorption of airborne hydrocarbons endowed these surfaces with excellent superhydrophobicity. We revealed by XPS that the adsorption of airborne hydrocarbons at the Ar + -etched clean Au surface was rather quick, such that organic contamination can hardly be prevented in practical operation of surface wetting investigation. We also confirmed by XPS that ultraviolet-O 3 treatment of the superhydrophobic metal surfaces did not remove the adsorbed hydrocarbons completely, but mainly oxidized them into hydrophilic oxygen-containing organic substances. We hope our findings here shed new light on deeper understanding of superhydrophobicity for micro/nanostructured metal surfaces with and without surface oxide films

  15. Escherichia coli as a potential hydrocarbon conversion microorganism. Oxidation of aliphatic and aromatic compounds by recombinant E. coli in two-liquid phase (aqueous-organic) systems

    NARCIS (Netherlands)

    Favre-Bulle, Olivier

    1992-01-01

    The increased interest in the study of hydrocarbon utilizing microorganisms in recent years has been stimulated by the possibility of using their monooxygenases in the selective oxidation of aliphatic and aromatic compounds. As an example, long chain (>C16) n-alkanes are converted to dicarboxylic

  16. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    Science.gov (United States)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  17. Diverse Reactions of Thiophenes, Selenophenes, and Tellurophenes with Strongly Oxidizing I(III) PhI(L)2 Reagents.

    Science.gov (United States)

    Egalahewa, Sathsara; Albayer, Mohammad; Aprile, Antonino; Dutton, Jason L

    2017-02-06

    We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr) 2 ][OTf] 2 (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr) 2 ][OTf] 2 gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.

  18. Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

    Directory of Open Access Journals (Sweden)

    Carlos Vila

    2014-05-01

    Full Text Available Pyrrolo[2,1-a]isoquinoline alkaloids have been prepared via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization cascade using Rose Bengal as an organo-photocatalyst. A variety of pyrroloisoquinolines have been obtained in good yields under mild and metal-free reaction conditions.

  19. Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

    Science.gov (United States)

    Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

    2013-04-01

    Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Diels-Alder reactions of inert aromatic compounds within a self-assembled coordination cage.

    Science.gov (United States)

    Horiuchi, Shinnosuke; Murase, Takashi; Fujita, Makoto

    2011-07-04

    A self-assembled coordination cage serves as a nanometer-sized molecular flask to promote the Diels-Alder reactions of aromatic hydrocarbons with N-cyclohexylmaleimide. The coordination cage accelerated the Diels-Alder reaction of anthracene at the electronically unfavorable, terminal benzene ring to give a compact, cavity-restrained syn-adduct. Activation-parameter measurements for the reactions revealed considerable reduction in the entropy cost, and preorganization of the substrates is a dominant factor in the enhanced reactivity. Owing to this entropy-cost reduction, otherwise-unreactive aromatic compounds, such as naphthalenes or triphenylene, also underwent Diels-Alder reactions in a regio- and stereocontrolled fashion. In the naphthalene Diels-Alder reaction, X-ray crystallographic analysis of the guest-inclusion complex clarified the reinforced orientation and proximity of the substrate pairs before the reaction. A perylene Diels-Alder adduct was stabilized inside the cage and protected from aerial oxidation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Fundamentals of Hydrocarbon Upgrading to Liquid Fuels and Commodity Chemicals over Catalytic Metallic Nanoparticles

    Science.gov (United States)

    Chen, Tao

    Promising new technologies for biomass conversion into fuels and chemical feedstocks rely on the production of bio-oils, which need to be upgraded in order to remove oxygen-containing hydrocarbons and water. A high oxygen concentration makes bio-oils acidic and corrosive, unstable during storage, and less energetically valuable per unit weight than petroleum-derived hydrocarbons. Although there are efficient processes for the production of bio-oils, there are no efficient technologies for their upgrading. Current technologies utilize traditional petroleum refining catalysts, which are not optimized for biomass processing. New upgrading technologies are, therefore, urgently needed for development of sustainable energy resources. Development of such new technologies, however, is severely hindered by a lack of fundamental understanding of how oxygen and oxygen-containing hydrocarbons derived from biomass interact with promising noble-metal catalysts. In this study, kinetic reaction measurements, catalyst characterization and quantum chemical calculations using density functional theory were combined for determining adsorption modes and reaction mechanisms of hydrocarbons in the presence of oxygen on surfaces of catalytic noble-metal nanoparticles. The results were used for developing improved catalyst formulations and optimization of reaction conditions. The addition of molybdenum to platinum catalysts was shown to improve catalytic activity, stability, and selectivity in hydrodeoxygenation of acetic acid, which served as a model biomass compound. The fundamental results that describe interactions of oxygen and hydrocarbons with noble-metal catalysts were extended to other reactions and fields of study: evaluation of the reaction mechanism for hydrogen peroxide decomposition, development of improved hydrogenation catalysts and determination of adsorption modes of a spectroscopic probe molecule.

  2. Kinetics and reaction mechanism for aminolysis of benzyl 4-pyridyl carbonate in H2O: Effect of modification of nucleofuge from 2-pyridyl oxide to 4-pyridyl oxide on reactivity and reaction mechanism

    International Nuclear Information System (INIS)

    Kang, Ji Sun; Um, Ikhwan

    2012-01-01

    Pseudo-first-order rate constants k amine have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in H 2 O at 25.0.deg.C. The plots of k amine vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate T ± and its deprotonated form T - . This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The k amine values for the reactions of 6 have been dissected into the second-order rate constant Kk 2 and the third order rate constant Kk 3 . The Brφnsted-type plots are linear with β nuc = 0.94 and 1.18 for Kk 2 and Kk 3 , respectively. The Kk 2 for the reaction of 6 is smaller than the second-order rate constant k N for the corresponding reaction of 5, although 4-pyridyl oxide in 6 is less basic and a better nucleofuge than 2-pyridyl oxide in 5

  3. Effects of gas flow on oxidation reaction in liquid induced by He/O{sub 2} plasma-jet irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Atsushi; Uchida, Giichiro, E-mail: uchida@jwri.osaka-u.ac.jp; Takenaka, Kosuke; Setsuhara, Yuichi [Joining and Welding Research Institute, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Kawasaki, Toshiyuki [Department of Mechanical and Electrical Engineering, Nippon Bunri University, Oita, Oita 870-0397 (Japan); Koga, Kazunori; Sarinont, Thapanut; Amano, Takaaki; Shiratani, Masaharu [Graduate School of Information Science and Electrical Engineering, Kyushu University, Fukuoka, Fukuoka 819-0395 (Japan)

    2015-07-28

    We present here analysis of oxidation reaction in liquid by a plasma-jet irradiation under various gas flow patterns such as laminar and turbulence flows. To estimate the total amount of oxidation reaction induced by reactive oxygen species (ROS) in liquid, we employ a KI-starch solution system, where the absorbance of the KI-starch solution near 600 nm behaves linear to the total amount of oxidation reaction in liquid. The laminar flow with higher gas velocity induces an increase in the ROS distribution area on the liquid surface, which results in a large amount of oxidation reaction in liquid. However, a much faster gas flow conversely results in a reduction in the total amount of oxidation reaction in liquid under the following two conditions: first condition is that the turbulence flow is triggered in a gas flow channel at a high Reynolds number of gas flow, which leads to a marked change of the spatial distribution of the ROS concentration in gas phase. Second condition is that the dimpled liquid surface is formed by strong gas flow, which prevents the ROS from being transported in radial direction along the liquid surface.

  4. Mass transfer model for two-layer TBP oxidation reactions

    International Nuclear Information System (INIS)

    Laurinat, J.E.

    1994-01-01

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development

  5. Oxidation of D-glucose and D-fructose with oxygen in aqueous, alkaline solutions. Part I. An integral reaction scheme

    NARCIS (Netherlands)

    de Wilt, H.G.J.; Kuster, B.F.M.

    1971-01-01

    The homogeneous oxidn. of D-glucose and D-fructose with O in aq., alk. solns. is studied, and a reaction scheme proposed to account for the obsd. reaction products. Formation of enolate anions is followed by non-oxidative reactions (involving double-bond migration and cleavage) and by oxidative

  6. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-01-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  7. Chemical reaction at ferromagnet/oxide interface and its influence on anomalous Hall effect

    International Nuclear Information System (INIS)

    Liu, Yi-Wei; Teng, Jiao; Zhang, Jing-Yan; Liu, Yang; Chen, Xi; Li, Xu-Jing; Feng, Chun; Wang, Hai-Cheng; Li, Ming-Hua; Yu, Guang-Hua; Wu, Zheng-Long

    2014-01-01

    Chemical reactions at the ferromagnet/oxide interface in [Pt/Fe] 3 /MgO and [Pt/Fe] 3 /SiO 2 multilayers before and after annealing were investigated by X-ray photoelectron spectroscopy. The results show that Fe atoms at the Fe/MgO interface were completely oxidized in the as-grown state and significantly deoxidized after vacuum annealing. However, only some of the Fe atoms at the Fe/SiO 2 interface were oxidized and rarely deoxidized after annealing. The anomalous Hall effect was modified by this interfacial chemical reaction. The saturation anomalous Hall resistance (R xy ) was greatly increased in the [Pt/Fe] 3 /MgO multilayers after annealing and was 350% higher than that in the as-deposited film, while R xy of the [Pt/Fe] 3 /SiO 2 multilayer only increased 10% after annealing.

  8. Contribution to the study of the oxidation reaction of the carbon oxide in contact with catalysts issued from the decomposition of nickel hydro-aluminates at various temperatures

    International Nuclear Information System (INIS)

    Samaane, Mikhail

    1966-01-01

    Addressing the study of the oxidation reaction of carbon oxide which produces carbon dioxide, this research thesis reports the study of this reaction in presence of catalysts (2NiO + Al 2 O 3 , NiAl 2 O 4 and NiO + NiAl 2 O 4 ) issued from the decomposition of nickel hydro-aluminates at different temperatures. The first part describes experimental techniques and the nature of materials used in this study. The second part reports the study of the catalytic activity of the 2NiO+Al 2 O 3 catalyst during the oxidation of CO. Preliminary studies are also reported: structure and texture of nickel hydro-aluminate which is the raw material used to produce catalysts, activation of this compound to develop the catalytic activity in CO oxidation, chemisorption of CO, O 2 and CO 2 on the 2NiO+Al 2 O 3 solid, interaction of adsorbed gases at the solid surface, and kinetic study of the oxidation reaction. The third part reports the study of the catalytic activity in the oxidation reaction of CO of spinel catalysts (NiAl 2 O 4 and NiO+NiAl 2 O 4 ) obtained by calcination of nickel hydro-aluminates at high temperature. The formation of the spinel phase, the chemisorption of CO, O 2 and CO 2 on NiAl 2 O 4 , and the kinetic of the oxidation reaction are herein studied

  9. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  10. Phenol by direct hydroxylation of benzene with nitrous oxide - role of surface oxygen species in the reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Reitzmann, A.; Klemm, E.; Emig, G. [Erlangen-Nuernberg Univ., Erlangen (Germany). Lehrstuhl fuer Technische Chemie 1; Buchholz, S.A.; Zanthoff, H.W. [Bochum Univ. (Germany). Inst. of Technical Chemistry

    1998-12-31

    Transient experiments in a Temporal Analysis of Products (TAP) Reactor were performed to elucidate the role of surface oyxgen species in the oxidation of benzene to phenol on ZSM-5 type zeolites with nitrous oxide as a selective oxidant. It was shown by puls experiments with nitrous oxide that the mean lifetime of the generated surface oxygen species is between 0.2s at 500 C and about 4.2 s at 400 C. Afterwards the surface oxygen species desorb as molecular oxygen into the gas phase where total oxidation will take place if hydrocarbons are present. Dual puls experiments consisting of a nitrous oxide puls followed by a benzene puls allowed studying the reactivity of the surface oxygen species formed during the first puls. The observation of the phenol formation was impeded due to the strong sorption of phenol. Multipulse experiments were necessary to reach a pseudo steady state phenol yield. (orig.)

  11. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  12. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Remediation of hydrocarbons in crude oil-contaminated soils using Fenton's reagent.

    Science.gov (United States)

    Ojinnaka, Chukwunonye; Osuji, Leo; Achugasim, Ozioma

    2012-11-01

    Sandy soil samples spiked with Bonny light crude oil were subsequently treated with Fenton's reagent at acidic, neutral, and basic pH ranges. Oil extracts from these samples including an untreated one were analyzed 1 week later with a gas chromatograph to provide evidence of hydrocarbon depletion by the oxidant. The reduction of three broad hydrocarbon groups-total petroleum hydrocarbon (TPH); benzene, toluene, ethylbenzene, and xylene (BTEX); and polycyclic aromatic hydrocarbon (PAH) were investigated at various pHs. Hydrocarbon removal was efficient, with treatment at the acidic pH giving the highest removal of about 96% for PAH, 99% for BTEX, and some TPH components experiencing complete disappearance. The four-ringed PAHs were depleted more than their three-ringed counterparts at the studied pH ranges.

  14. Biogeochemistry of Halogenated Hydrocarbons

    Science.gov (United States)

    Adriaens, P.; Gruden, C.; McCormick, M. L.

    2003-12-01

    Halogenated hydrocarbons originate from both natural and industrial sources. Whereas direct anthropogenic emissions to the atmosphere and biosphere are often easy to assess, particularly when they are tied to major industrial activities, the attribution of emissions to other human activities (e.g., biomass burning), diffuse sources (e.g., atmospheric discharge, run off), and natural production (e.g., soils, fungi, algae, microorganisms) are difficult to quantify. The widespread occurrence of both alkyl and aryl halides in groundwater, surface water, soils, and various trophic food chains, even those not affected by known point sources, suggests a substantial biogeochemical cycling of these compounds (Wania and Mackay, 1996; Adriaens et al., 1999; Gruden et al., 2003). The transport and reactive fate mechanisms controlling their reactivity are compounded by the differences in sources of alkyl-, aryl-, and complex organic halides, and the largely unknown impact of biogenic processes, such as enzymatically mediated halogenation of organic matter, fungal production of halogenated hydrocarbons, and microbial or abiotic transformation reactions (e.g., Asplund and Grimvall, 1991; Gribble, 1996; Watling and Harper, 1998; Oberg, 2002). The largest source may be the natural halogenation processes in the terrestrial environment, as the quantities detected often exceed the amount that can be explained by human activities in the surrounding areas ( Oberg, 1998). Since biogeochemical processes result in the distribution of a wide range of halogenated hydrocarbon profiles, altered chemical structures, and isomer distributions in natural systems, source apportionment (or environmental forensics) can often only be resolved using multivariate statistical methods (e.g., Goovaerts, 1998; Barabas et al., 2003; Murphy and Morrison, 2002).This chapter will describe the widespread occurrence of halogenated hydrocarbons, interpret their distribution and biogeochemical cycling in light of

  15. Covalently Bonded Chitosan on Graphene Oxide via Redox Reaction

    Directory of Open Access Journals (Sweden)

    Víctor M. Castaño

    2013-03-01

    Full Text Available Carbon nanostructures have played an important role in creating a new field of materials based on carbon. Chemical modification of carbon nanostructures through grafting has been a successful step to improve dispersion and compatibility in solvents, with biomolecules and polymers to form nanocomposites. In this sense carbohydrates such as chitosan are extremely valuable because their functional groups play an important role in diversifying the applications of carbon nanomaterials. This paper reports the covalent attachment of chitosan onto graphene oxide, taking advantage of this carbohydrate at the nanometric level. Grafting is an innovative route to modify properties of graphene, a two-dimensional nanometric arrangement, which is one of the most novel and promising nanostructures. Chitosan grafting was achieved by redox reaction using different temperature conditions that impact on the morphology and features of graphene oxide sheets. Transmission Electron Microscopy, Fourier Transform Infrared, Raman and Energy Dispersive spectroscopies were used to study the surface of chitosan-grafted-graphene oxide. Results show a successful modification indicated by the functional groups found in the grafted material. Dispersions of chitosan-grafted-graphene oxide samples in water and hexane revealed different behavior due to the chemical groups attached to the graphene oxide sheet.

  16. Microbial production of gaseous hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Fukuda, Hideo

    1987-10-20

    Microbial production of ethylene, isobutane and a saturated gaseous hydrocarbon mixture was described. Microbial ethylene production was studied with Penicillium digitatum IFO 9372 and a novel pathway of the ethylene biosynthesis through alpha-ketoglutarate was proposed. Rhodotorula minuta IFO 1102 was selected for the microbial production of isobutane and the interesting actions of L-leucine and L-phenylalanine for the isobutane production were found. It was finally presented about the microbial production of a saturated gaseous hydrocarbon mixture with Rhizopus japonicus IFO 4758 was described. A gas mixture was produced through a chemical reaction of SH compounds and some cellular component such as squalene under aerobic conditions. (4 figs, 7 tabs, 41 refs)

  17. Catalytic treatment of hydrocarbon oils

    Energy Technology Data Exchange (ETDEWEB)

    1940-02-23

    A process is described for increasing the octane number of a hydrocarbon oil. The substance is subjected under pressure to a temperature between 800 and 1100/sup 0/C. Catalysts include metal compounds of Groups IV, V, Vi, or VIII (Group VI is perferred). Experiments are performed under a hydrogen atmosphere. Reaction time, temperature, pressure, and partial pressure of the hydrogen are adjusted so that there will be no net hydrogen consumption. The reaction gases (including the products) are recycled in whole or in part to supply the hydrogen gas required.

  18. Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides

    Science.gov (United States)

    Taatjes, Craig A.

    2017-05-01

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

  19. Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

    Science.gov (United States)

    Wang, Shunyao; Ye, Jianhuai; Soong, Ronald; Wu, Bing; Yu, Legeng; Simpson, André J.; Chan, Arthur W. H.

    2018-03-01

    Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal-organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

  20. Composition and method for coke retardant during hydrocarbon processing

    International Nuclear Information System (INIS)

    Reid, D.K.

    1988-01-01

    A process is described for inhibiting the formation and deposition of filamentous coke on metallic surfaces in contact with a hydrocarbon having a temperature of 600 0 -1300 0 F which comprises adding to the hydrocarbon a sufficient amount for the purpose of a boron compound selected from the group of boron oxide compounds, boric acid and metal borides, with the proviso that when boric acid is used, it is substantially free of water

  1. Insights into hydrocarbon formation by nitrogenase cofactor homologs.

    Science.gov (United States)

    Lee, Chi Chung; Hu, Yilin; Ribbe, Markus W

    2015-04-14

    The L-cluster is an all-iron homolog of nitrogenase cofactors. Driven by europium(II) diethylenetriaminepentaacetate [Eu(II)-DTPA], the isolated L-cluster is capable of ATP-independent reduction of CO and CN(-) to C1 to C4 and C1 to C6 hydrocarbons, respectively. Compared to its cofactor homologs, the L-cluster generates considerably more CH4 from the reduction of CO and CN(-), which could be explained by the presence of a "free" Fe atom that is "unmasked" by homocitrate as an additional site for methanation. Moreover, the elevated CH4 formation is accompanied by a decrease in the amount of longer hydrocarbons and/or the lengths of the hydrocarbon products, illustrating a competition between CH4 formation/release and C-C coupling/chain extension. These observations suggest the possibility of designing simpler synthetic clusters for hydrocarbon formation while establishing the L-cluster as a platform for mechanistic investigations of CO and CN(-) reduction without complications originating from the heterometal and homocitrate components. Nitrogenase is a metalloenzyme that is highly complex in structure and uniquely versatile in function. It catalyzes two reactions that parallel two important industrial processes: the reduction of nitrogen to ammonia, which parallels the Haber-Bosch process in ammonia production, and the reduction of carbon monoxide to hydrocarbons, which parallels the Fischer-Tropsch process in fuel production. Thus, the significance of nitrogenase can be appreciated from the perspective of the useful products it generates: (i) ammonia, the "fixed" nitrogen that is essential for the existence of the entire human population; and (ii) hydrocarbons, the "recycled" carbon fuel that could be used to directly address the worldwide energy shortage. This article provides initial insights into the catalytic characteristics of various nitrogenase cofactors in hydrocarbon formation. The reported assay system provides a useful tool for mechanistic

  2. Mineral-assisted production of benzene under hydrothermal conditions: Insights from experimental studies on C6 cyclic hydrocarbons

    Science.gov (United States)

    Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando

    2017-10-01

    Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this

  3. Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

    Science.gov (United States)

    Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

    2018-01-01

    In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

  4. Gas-Solid Reaction Route toward the Production of Intermetallics from Their Corresponding Oxide Mixtures

    Directory of Open Access Journals (Sweden)

    Hesham Ahmed

    2016-08-01

    Full Text Available Near-net shape forming of metallic components from metallic powders produced in situ from reduction of corresponding pure metal oxides has not been explored to a large extent. Such a process can be probably termed in short as the “Reduction-Sintering” process. This methodology can be especially effective in producing components containing refractory metals. Additionally, in situ production of metallic powder from complex oxides containing more than one metallic element may result in in situ alloying during reduction, possibly at lower temperatures. With this motivation, in situ reduction of complex oxides mixtures containing more than one metallic element has been investigated intensively over a period of years in the department of materials science, KTH, Sweden. This review highlights the most important features of that investigation. The investigation includes not only synthesis of intermetallics and refractory metals using the gas solid reaction route but also study the reaction kinetics and mechanism. Environmentally friendly gases like H2, CH4 and N2 were used for simultaneous reduction, carburization and nitridation, respectively. Different techniques have been utilized. A thermogravimetric analyzer was used to accurately control the process conditions and obtain reaction kinetics. The fluidized bed technique has been utilized to study the possibility of bulk production of intermetallics compared to milligrams in TGA. Carburization and nitridation of nascent formed intermetallics were successfully carried out. A novel method based on material thermal property was explored to track the reaction progress and estimate the reaction kinetics. This method implies the dynamic measure of thermal diffusivity using laser flash method. These efforts end up with a successful preparation of nanograined intermetallics like Fe-Mo and Ni-W. In addition, it ends up with simultaneous reduction and synthesis of Ni-WN and Ni-WC from their oxide mixtures

  5. A combinatorial chemistry approach to the investigation of cerium oxide and plutonium oxide reactions with small molecules

    Science.gov (United States)

    Brady, John T.; Warner, Benjamin P.; Bridgewater, Jon S.; Havrilla, George J.; Morris, David E.; Buscher, C. Thomas

    2000-07-01

    We are currently investigating the potential chemistry of the 3013 Standard waste storage containers. These containers are filled with waste that is a mixture of inorganic salts and plutonium oxide that has been calcined to remove water and other volatiles. There has been concern about possible pressure buildup due to the formation of hydrogen or other gases. We are utilizing a combinatorial chemistry approach to investigate a range of possible reactions that may occur in the containers with various concentrations of metal oxides and inorganic salts.

  6. Propan-1-ol Oxidation Reaction on Au/TiO2 Catalysts

    African Journals Online (AJOL)

    MBI

    2014-11-27

    Nov 27, 2014 ... a decomposition pathway, producing CO2 and H2O. However, the presence of gold ... complete oxidation reaction of propan-1-ol on the catalysts. Keywords: Gold Catalysis ... flowed at a rate of 30 mL min-1. Propan- o-l was.

  7. Fenton's reagent as a remediation process in water treatment: application to the degradation of polycyclic aromatic hydrocarbons in waters and sewage sludges; La reaction de fenton comme procede de rehabilitation dans le traitement des eaux: application a la degradation des hydrocarbures aromatiques polycycliques dans les eaux et les boues residuaires

    Energy Technology Data Exchange (ETDEWEB)

    Flotron, V

    2004-05-15

    This study is related to the application of Fenton's reagent to remedy matrices contaminated by polycyclic aromatic hydrocarbons (PAHs). In aqueous solution, the choice of the reagent implementation is important, in order to generate enough radicals to oxidize pollutants. Degradation of the organic compounds is possible, but a large difference in reactivity is observed between 'alternant' and 'non-alternant' PAHs (with a five carbon atoms cycle). Besides, if a few specific precautions are omitted, the PAHs can sorb onto the flask inside surface, and therefore not undergo oxidation. The results on sewage sludges show that under certain conditions (high reagent concentrations), the pollutants can be oxidised although they are adsorbed. Moreover, it appears that the matrix itself plays an important role, as the iron oxides seem to be able to decompose hydrogen peroxide, and thus initiate Fenton reaction. Its application to contaminated soils and sediments is also possible. (author)

  8. Chemical oxidizers treat wastewater

    International Nuclear Information System (INIS)

    Stephenson, F.A.

    1992-01-01

    Based on the inherent benefits of these original oxidation systems, a second generation of advanced oxidation processes (AOPs) has emerged. These processes combine key features of the first generation technologies with more sophisticated advances in UV technology, such as the new pulsed plasma xenon flash lamp that emits high-energy, high-intensity UV light. Second generation systems can be equipped with a transmittance controller to prevent lamp fouling or scaling. The coupling of the first generation's technology with the new UV sources provides the rapid destruction of chlorinated and nonchlorinated hydrocarbons and humic acids from contaminated water. It also is effective in the treatment of organic laden gases from soil vapor extraction systems. AOPs may promote the oxidation (and subsequent removal) of heavy metals in water, though few data are available to verify the claim. The success of AOPs, including ozonation with UV light, hydrogen peroxide with UV light and advanced photolysis, is linked with their creation of hydroxyl-free radicals (OH·) that are effective in eliminating contaminants such as formaldehyde, chlorinated hydrocarbons and chlorinated solvents. Hydroxyl free-radicals are consumed in microsecond reactions and exhibit little substrate selectivity with the exception of halogenated alkanes such as chloroform. They can act as chain carriers. Given their power, hydroxyl free-radicals react with virtually all organic solutes more quickly (especially in water) than any other oxidants, except fluorine. There are projects that have found the combination of some AOPs to be the most efficient organic destruction techniques for the job. For example, one project successfully remediated groundwater contaminated with gasoline and Number 2 diesel through successive treatments of ozone and hydrogen peroxide with ultraviolet light, followed by granular activated carbon. 5 refs., 2 tabs

  9. Tin-antimony oxide oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

    1998-12-15

    Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

  10. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto; Menendez Rodriguez, Gabriel; Bellachioma, Gianfranco; Zuccaccia, Cristiano; Poater, Albert; Cavallo, Luigi; Macchioni, Alceo

    2016-01-01

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  11. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  12. Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

    International Nuclear Information System (INIS)

    Ahmed, I.I.; Gupta, A.K.

    2012-01-01

    Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

  13. Formation of polycyclic aromatic hydrocarbons by ionizing radiations

    International Nuclear Information System (INIS)

    Perez, G.; Lilia, E.; Cristalli, A.

    1986-01-01

    Gaseous 0-terphenyl, 1-phenylnaphthalene, and 9-phenylanthracene were submitted to gamma rays. The yields of cyclization products, polycyclic aromatic hydrocarbons, show that at least one twentieth of the intermediates formed undergo intramolecular reaction. (author)

  14. Interactions between marine bacteria and dissolved-phase and beached hydrocarbons after the Exxon Valdez oil spill

    International Nuclear Information System (INIS)

    Button, D.K.; Robertson, B.R.; McIntosh, D.; Juettner, F.

    1992-01-01

    Turnover times for toluene in Resurrection Bay after the Exxon Valdez grounding were determined to be decades, longer than expected considering that dissolved hydrocarbons were anticipated to drift with the current and stimulate development of additional hydrocarbon-utilizing capacity among the microflora in that downcurrent location. These turnover times were based on the recovery of 14 CO 2 from added [ 14 C]toluene that was oxidized. The concentrations of toluene there, 0.1 to 0.2 μg/liter, were similar to prespill values. Oxidation rates appeared to be enhanced upstream near islands in the wake of the wind-blown slick, and even more within the slick itself. Since current-driven mixing rates exceeded those of oxidation, dissolved spill components such as toluene should enter the world-ocean pool of hydrocarbons rather than biooxidize in place. Some of the floating oil slick washed ashore and permeated a coarse gravel beach. A bacterial biomass of 2 to 14 mg/kg appeared in apparent response to the new carbon and energy source. A large population of carbon- and energy-starved, induced hydrocarbon oxidizers with metabolism limited by the physical and molecular recalcitrance of the heavier components is suggested. The effects of a surfactant that was widely applied were unremarkable on a test beach after 1.5 months. Unresolved components appearing in chromatograms from the remaining mixture were characteristic of partial oxidation products. Such compounds, known to accumulate when concentrations of smaller aqueous-phase hydrocarbons exceed the K m , may form in sediments as well

  15. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull [Yeungnam University, Gyeongsan (Korea, Republic of)

    2016-02-15

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  16. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    International Nuclear Information System (INIS)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull

    2016-01-01

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  17. A comparative DFT study on CO oxidation reaction over Si-doped BC2N nanosheet and nanotube

    Science.gov (United States)

    Nematollahi, Parisa; Neyts, Erik C.

    2018-05-01

    In this study, we performed density functional theory (DFT) calculations to investigate different reaction mechanisms of CO oxidation catalyzed by the Si atom embedded defective BC2N nanostructures as well as the analysis of the structural and electronic properties. The structures of all the complexes are optimized and characterized by frequency calculations at the M062X/6-31G∗ computational level. Also, The electronic structures and thermodynamic parameters of adsorbed CO and O2 molecules over Si-doped BC2N nanostructures are examined in detail. Moreover, to investigate the curvature effect on the CO oxidation reaction, all the adsorption and CO oxidation reactions on a finite-sized armchair (6,6) Si-BC2NNT are also studied. Our results indicate that there can be two possible pathways for the CO oxidation with O2 molecule: O2(g) + CO(g) → O2(ads) + CO(ads) → CO2(g) + O(ads) and O(ads) + CO(g) → CO2(g). The first reaction proceeds via the Langmuir-Hinshelwood (LH) mechanism while the second goes through the Eley-Rideal (ER) mechanism. On the other hand, by increasing the tube diameter, the energy barrier increases due to the strong adsorption energy of the O2 molecule which is related to its dissociation over the tube surface. Our calculations indicate that the two step energy barrier of the oxidation reaction over Si-BC2NNS is less than that over the Si-BC2NNT. Hence, Si-BC2NNS may serve as an efficient and highly activated substrate to CO oxidation rather than (4,4) Si-BC2NNT.

  18. A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

    Science.gov (United States)

    Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

    2018-06-01

    The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

  19. Modification of Catalysts for Steam Reforming of Fluid Hydrocarbons. Research of Gas-Dynamic Duct Cooling Using Planar and Framework Catalysts (CD-ROM)

    National Research Council Canada - National Science Library

    Kuranov, Alexander L

    2005-01-01

    .... One way of fuel conversion is the catalytic steam reforming of hydrocarbon. This reaction has a large heat capacity and gives maximum quantity of molecular hydrogen among known reactions of hydrocarbons...

  20. Tuning the two-dimensional electron liquid at oxide interfaces by buffer-layer-engineered redox reactions

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Green, Robert J.; Sutarto, Ronny

    2017-01-01

    Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO3 (STO) achieved using polar La7/8Sr1/8MnO3 (LSMO) buffer layers to manipulate both...... polarities and redox reactions from disordered overlayers grown at room temperature. Using resonant x-ray reflectometry experiments, we quantify redox reactions from oxide overlayers on STO as well as polarity induced electronic reconstruction at epitaxial LSMO/STO interfaces. The analysis reveals how...... these effects can be combined in a STO/LSMO/disordered film trilayer system to yield high mobility modulation doped 2DELs, where the buffer layer undergoes a partial transformation from perovskite to brownmillerite structure. This uncovered interplay between polar discontinuities and redox reactions via buffer...

  1. Reaction modelling of Iron Oxide Bromination in the UT-3 thermochemical cycle for Hydrogen production from water

    International Nuclear Information System (INIS)

    Amir-Rusli

    1996-01-01

    Analysis modelling of the iron oxide bromination had been carried out using experiment data from the iron oxide bromination in the UT-3 thermochemical cycle. Iron oxide in the form of pellets were made of the calcination of the mixture of iron oxide, silica, graphite and cellulose at 1473 K. Thermobalance reactor was used to study the kinetic reactions of the iron oxide bromination at a temperature of 473 K for 2 - 6 hours. The data collected from the experiments were used as input for the common models. However, none of these models could not explain the result of the experiments. A new model, a combination of two kinetic reactions : exposed particle and coated particle was created and worked successfully

  2. Complete oxidation of 1,2-dichlorobenzene over V{sub 2}O{sub 5}-TiO{sub 2} and MnO{sub x}-TiO{sub 2} aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jinsoon [Research Institute of Industrial Science and Technology, Pohang (Korea, Republic of); Suh, Dong Jin [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2014-10-15

    Catalytic destruction of 1,2-dichlorobenzene was carried out over two types of aerogels, vanadia-titania and manganese oxide-titania. Reactions were performed in a plug flow reactor in the range of 150-600 .deg. C. Both catalysts resulted in very high selectivity to carbon oxides and produced negligible amount of hydrocarbon byproducts. Over the vanadia-titania catalysts, the chlorinated compound was relatively more efficiently destructed at lower temperature, while selectivity towards carbon dioxide was much higher over manganese oxide-titania aerogel catalysts. Regardless of the preparation methods, showed a tendency to produce carbon monoxide with 35-45% selectivity throughout the reaction temperature range while manganese oxide-titania exhibited more than 90% CO{sub 2} selectivity at above 400 .deg. C.

  3. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Burke, Michael P.; Goldsmith, C. Franklin; Klippenstein, Stephen J.; Welz, Oliver; Huang, Haifeng; Antonov, Ivan O.; Savee, John D.; Osborn, David L.; Zádor, Judit; Taatjes, Craig A.; Sheps, Leonid

    2015-07-16

    We have developed a multi-scale approach (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547–555.) to kinetic model formulation that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation to unexplored conditions. Here, we extend and generalize the multi-scale modeling strategy to treat systems of considerable complexity – involving multi-well reactions, potentially missing reactions, non-statistical product branching ratios, and non-Boltzmann (i.e. non-thermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multi-scale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both “parametric” and “structural” uncertainties. Theoretical parameters (e.g. barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g. initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multi-scale informed

  4. Evaluation of the kinetic and thermodynamic parameters of oxidation reaction in biodiesel from a quaternary mixture of raw material

    Directory of Open Access Journals (Sweden)

    Karina Gomes Angilelli

    2017-05-01

    Full Text Available A mixture of vegetable oil and animal fat as raw materials was optimized by simplex-centroid mixture design to produce a type of biodiesel with good oxidative stability, flow properties and reaction yield. Further, kinetic and thermodynamic parameters of oxidation reaction were determined by the accelerated method at different temperatures. Biodiesel produced with sodium methoxide as catalyst presented 6.5°C of cloud point, 2.0°C of pour point, and oxidative stability at 110°C equal to 8.98h, with a reaction yield of 96.04%. Activation energy of the oxidation reaction was 81.03 kJ mol-1 for biodiesel produced with sodium hydroxide and 90.51 kJ mol-1 for sodium methoxide. The positive values for DH‡ and DG‡ indicate that the oxidation process is endothermic and endergonic. The less negative DS‡ for biodiesel produced with sodium methoxide (-28.87 JK-1 mol-1 showed that the process of degradation of this biofuel was slower than that produced with NaOH. The mixture of raw materials proposed, transesterified with the methoxide catalyst, resulted in a biofuel that resisted oxidation for longer periods, making unnecessary the addition of antioxidant

  5. The analysis of magnesium oxide hydration in three-phase reaction system

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin, E-mail: ntp@dlmu.edu.cn

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

  6. Autothermal reforming of liquid hydrocarbons for H{sub 2} production

    Energy Technology Data Exchange (ETDEWEB)

    Palm, C.; Montel, S.; Cremer, P.; Peters, R.; Stolten, D. [Forschungszentrum Juelich GmbH (Germany). Inst. for Materials and Processes in Energy Systems IWV-3: Process Engineering

    2001-07-01

    The process of autothermal reforming of hydrocarbons can be used for the production of hydrogen within a fuel cell system. The application of three precious metal catalysts for the autothermal reforming of alkane mixtures with boiling ranges between 235 and 325 C was examined. The experiments were carried out at n(O{sub 2})/n(C) = 0.40, n(H{sub 2}O)/n(C) = 2.20, a catalyst bed temperature between 730 and 570 C and a hydrocarbon feed of 30 g/h. The catalysts yielded different hydrocarbon conversions, which can be explained by differences in the activity for the steam reforming reaction. The most active catalyst was also successfully utilized in the conversion of 400 g/h hydrocarbon feed. (orig.)

  7. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  8. Antioxidant Functions of the Aryl Hydrocarbon Receptor

    Directory of Open Access Journals (Sweden)

    Cornelia Dietrich

    2016-01-01

    Full Text Available The aryl hydrocarbon receptor (AhR is a transcription factor belonging to the basic helix-loop-helix/PER-ARNT-SIM family. It is activated by a variety of ligands, such as environmental contaminants like polycyclic aromatic hydrocarbons or dioxins, but also by naturally occurring compounds and endogenous ligands. Binding of the ligand leads to dimerization of the AhR with aryl hydrocarbon receptor nuclear translocator (ARNT and transcriptional activation of several xenobiotic phase I and phase II metabolizing enzymes. It is generally accepted that the toxic responses of polycyclic aromatic hydrocarbons, dioxins, and structurally related compounds are mediated by activation of the AhR. A multitude of studies indicate that the AhR operates beyond xenobiotic metabolism and exerts pleiotropic functions. Increasing evidence points to a protective role of the AhR against carcinogenesis and oxidative stress. Herein, I will highlight data demonstrating a causal role of the AhR in the antioxidant response and present novel findings on potential AhR-mediated antioxidative mechanisms.

  9. QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

    Science.gov (United States)

    Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

    2017-03-22

    Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

  10. Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

    Science.gov (United States)

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-06-01

    Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H 2 , quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Concentrated Aqueous Sodium Tosylate as Green Medium for Alkene Oxidation and Nucleophilic Substitution Reactions.

    Science.gov (United States)

    Sela, Tal; Lin, Xiaoxi; Vigalok, Arkadi

    2017-11-03

    A hydrotropic solution of highly concentrated sodium tosylate (NaOTs) can be used as a recyclable medium for the environmentally benign oxidation of conjugated alkenes with H 2 O 2 . Both uncatalyzed and metal-catalyzed reactions provided the corresponding oxidation products in higher yields than in pure water or many common organic solvents.

  12. Development of a redox-free Mitsunobu reaction exploiting phosphine oxides as precursors to dioxyphosphoranes.

    Science.gov (United States)

    Tang, Xiaoping; Chapman, Charlotte; Whiting, Matthew; Denton, Ross

    2014-07-14

    The development of the first redox-free protocol for the Mitsunobu reaction is described. This has been achieved by exploiting triphenylphosphine oxide--the unwanted by-product in the conventional Mitsunobu reaction--as the precursor to the active P(V) coupling reagent. Multinuclear NMR studies are consistent with hydroxyl activation via an alkoxyphosphonium salt.

  13. Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene

    International Nuclear Information System (INIS)

    Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Chen, Jianmin; Wang, Wenxing

    2014-01-01

    The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72 × 10 −11 cm 3 molecule −1 s −1 at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion. - Highlights: • We studied a comprehensive mechanism of OH-initiated oxidation of fluoranthene. • We reported the formation pathways of fluoranthone, fluoranthenequinone and epoxide. • The rate constants of the crucial elementary steps were evaluated

  14. Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene

    Energy Technology Data Exchange (ETDEWEB)

    Dang, Juan; Shi, Xiangli; Zhang, Qingzhu, E-mail: zqz@sdu.edu.cn; Hu, Jingtian; Chen, Jianmin; Wang, Wenxing

    2014-08-15

    The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72 × 10{sup −11} cm{sup 3} molecule{sup −1} s{sup −1} at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion. - Highlights: • We studied a comprehensive mechanism of OH-initiated oxidation of fluoranthene. • We reported the formation pathways of fluoranthone, fluoranthenequinone and epoxide. • The rate constants of the crucial elementary steps were evaluated.

  15. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

    International Nuclear Information System (INIS)

    Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.

    2014-01-01

    Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

  16. GC×GC measurements of C7-C11 aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

    Directory of Open Access Journals (Sweden)

    X. Xu

    2003-01-01

    Full Text Available During the Mediterranean Intensive Oxidant Study (MINOS campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene to 43±36 pptv (toluene. The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and

  17. Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst : Factors affecting the Rate of Total Oxidation of Ethane and Ethylene

    NARCIS (Netherlands)

    Roos, J.A.; Korf, S.J.; Veehof, R.H.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    Experiments using gas mixtures of O2, C2H6 or C2H4 and CH4 or He have been carried out with a Li/MgO catalyst using a well-mixed reaction system which show that the total oxidation products, CO and CO2, are formed predominantly from ethylene, formed in the oxidative coupling of methane. It is

  18. One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

    Science.gov (United States)

    Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

    2014-02-21

    In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

  19. Air injection low temperature oxidation process for enhanced oil recovery from light oil reservoirs

    International Nuclear Information System (INIS)

    Tunio, A.H.; Harijan, K.

    2010-01-01

    This paper represents EOR (Enhanced Oil Recovery) methods to recover unswept oil from depleted light oil reservoirs. The essential theme here is the removal of oxygen at LTO (Low Temperature Oxidation) from the injected air for a light oil reservoir by means of some chemical reactions occurring between oil and oxygen. In-situ combustion process, HTO (High Temperature Oxidation) is not suitable for deep light oil reservoirs. In case of light oil reservoirs LTO is more suitable to prevail as comparative to HTO. Few laboratory experimental results were obtained from air injection process, to study the LTO reactions. LTO process is suitable for air injection rate in which reservoir has sufficiently high temperature and spontaneous reaction takes place. Out comes of this study are the effect of LTO reactions in oxygen consumption and the recovery of oil. This air injection method is economic compared to other EOR methods i.e. miscible hydrocarbon gas, nitrogen, and carbon dioxide flooding etc. This LTO air injection process is suitable for secondary recovery methods where water flooding is not feasible due to technical problems. (author)

  20. Catalytic oxidation using nitrous oxide

    Directory of Open Access Journals (Sweden)

    Juan Carlos Beltran-Prieto

    2017-01-01

    Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

  1. Chemical deactivation of Ag/Al2O3 by sulphur for the selective reduction of NOx using hydrocarbons

    International Nuclear Information System (INIS)

    Houel, Valerie; Millington, Paul; Pollington, Stephen; Poulston, Stephen; Rajaram, Raj R.; Tsolakis, Athanasios

    2006-01-01

    The hydrocarbon-SCR activity of Ag/Al 2 O 3 catalysts is severely deactivated after low temperature (350 o C) sulphur ageing in the form of SO 2 exposure. Catalysts aged with SO 2 , NO and hydrocarbon present accumulate a significantly larger amount of SO 4 2- than those aged in the presence of only O 2 , H 2 O and SO 2 when exposed to an equivalent amount of S. Following sulphation of the catalyst most of the sulphur can be removed by a high temperature (600 o C) treatment in the reaction gas. Regeneration in the absence of hydrocarbon is ineffective. The hydrocarbon-SCR activity of the sulphated catalyst using model hydrocarbons such as n-C 8 H 18 can be restored after a high temperature pre-treatment in the reaction gases. However this desulphation process fails to regenerate the hydrocarbon-SCR activity when diesel fuel is used in the activity test. TPR studies show that a major fraction of the sulphur species present in the catalyst is removed by such pre-treatment, but the slight residual amount of sulphur is sufficient to inhibit the activation of the diesel fuel on the Ag catalyst. The nature of the hydrocarbon species present for the hydrocarbon-SCR reaction and during the regeneration strongly influences the activity. In general aromatics such as C 7 H 8 are less effective for reducing NO x and regenerating the sulphated catalyst. (author)

  2. A short synthesis-stuttgart of (S)-pyrrolam A via domino oxidation-witting reaction

    Digital Repository Service at National Institute of Oceanography (India)

    Majik, M.S.; Shet, J.; Tilve, S.G.; Parameswaran, P.S.

    A short synthesis of (S)-pyrrolam A starting from readily available N-(benzyloxycarbonyl)-L prolinol is described that makes use of a domino primary alcohol oxidation-Witting reaction as the key step...

  3. Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

    Science.gov (United States)

    Wang, Jun; Chen, Zaiming; Chen, Baoliang

    2014-05-06

    The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

  4. NOxTOy: A miniaturised new instrument for reactive nitrogen oxides in the atmosphere

    International Nuclear Information System (INIS)

    Dommen, J.; Prevot, A.S.H.; Neininger, B.; Clark, N.

    2000-01-01

    Emission of nitrogen oxides (NO, NO 2 ) and hydrocarbons into the atmosphere lead, under sunlight, to the formation of ozone and other photo oxidants. To better understand the ozone forming processes, the production and concentration of the nitrogen containing reaction products like nitric acid (HNO 3 ) or peroxyacetylnitrate (PAN) have to be determined. In a joint project with other research institutions and a private enterprise a miniaturised instrument was developed under a KTI contract. It is possible to measure several nitrogen oxides, NO 2 , NO x , NO y , PAN, HNO 3 and O x simultaneously. The dimensions and the power consumption of the instrument are suited for the operation in a motor glider and in a van. First measurements have been successfully performed and are presented. (authors)

  5. Storage stability of cauliflower soup powder: The effect of lipid oxidation and protein degradation reactions.

    Science.gov (United States)

    Raitio, Riikka; Orlien, Vibeke; Skibsted, Leif H

    2011-09-15

    Soups based on cauliflower soup powders, prepared by dry mixing of ingredients and rapeseed oil, showed a decrease in quality, as evaluated by a sensory panel, during the storage of the soup powder in the dark for up to 12weeks under mildly accelerated conditions of 40°C and 75% relative humidity. Antioxidant, shown to be effective in protecting the rapeseed bulk oil, used for the powder preparation, had no effect on storage stability of the soup powder. The freshly prepared soup powder had a relatively high concentration of free radicals, as measured by electron spin resonance spectroscopy, which decreased during storage, and most remarkably during the first two weeks of storage, with only marginal increase in lipid hydroperoxides as primary lipid oxidation products, and without any increase in secondary lipid oxidation products. Analyses of volatiles by SPME-GC-MS revealed a significant increase in concentrations of 2-methyl- and 3-methyl butanals, related to Maillard reactions, together with an increase in 2-acetylpyrrole concentration. The soup powders became more brown during storage, as indicated by a decreasing Hunter L-value, in accord with non-enzymatic browning reactions. A significant increase in the concentrations of dimethyl disulfide in soup powder headspace indicated free radical-initiated protein oxidation. Protein degradation, including Maillard reactions and protein oxidation, is concluded to be more important than lipid oxidation in determining the shelf-life of dry cauliflower soup powder. Copyright © 2011 Elsevier Ltd. All rights reserved.

  6. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    International Nuclear Information System (INIS)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

  7. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  8. Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

    Energy Technology Data Exchange (ETDEWEB)

    Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

    2014-10-28

    developed Reactive Force Field (ReaxFF) to study interaction of the targeted POMs with water, proton and hydroxide ions in the liquid phase. We tested our ReaxFF parameters on the Lindqvist POMs, M6O19n-, where M = Nb and Ta. These parameters are made available as part of the ReaxFF code. In addition, we have developed parameters for Sc, Ti, Fe, Co and Ni in combination with H, C, N, O, as well as the same metal (M-M) for the spin-polarized self-consistent-charge density-functional tight-binding (DFTB) method. Test calculations showed that the DFTB method with the present parameters in most cases reproduces structural properties very well. These parameters are made available as part of the DFTB code. Thus, this DOE BES funded research project has clarified several key areas impacting (a) water oxidation and O2-based hydrocarbon transformation, (b) stabilization of key structures and catalytic intermediates in such processes, (c) immobilization of molecular catalysts on metal oxide surfaces, and (d) application of optimal computational methods to study reaction dynamics in large systems.

  9. Hantzsch Reaction Starting Directly from Alcohols through a Tandem Oxidation Process

    Directory of Open Access Journals (Sweden)

    Xiaobing Liu

    2017-01-01

    Full Text Available A Brønsted acidic ionic liquid, 3-(N,N-dimethyldodecylammonium propanesulfonic acid hydrogen sulphate ([DDPA][HSO4], has been successfully applied to catalyze sequential oxidation of aromatic alcohols with NaNO3 followed by their condensation with dicarbonyl compound and ammonium acetate. The corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines could be obtained as a major product with high yields by the multicomponent reaction. The present work utilizing alcohols instead of aldehyde in Hantzsch reaction is a valid and green alternative to the classical synthesis of the corresponding pyridine analogues of Hantzsch 1,4-dihydropyridines.

  10. Cracking hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Forwood, G F; Lane, M; Taplay, J G

    1921-10-07

    In cracking and hydrogenating hydrocarbon oils by passing their vapors together with steam over heated carbon derived from shale, wood, peat or other vegetable or animal matter, the gases from the condenser are freed from sulfuretted hydrogen, and preferably also from carbon dioxide, and passed together with oil vapors and steam through the retort. Carbon dioxide may be removed by passage through slaked lime, and sulfuretted hydrogen by means of hydrated oxide of iron. Vapors from high-boiling oils and those from low-boiling oils are passed alternately through the retort, so that carbon deposited from the high-boiling oils is used up during treatment of low-boiling oils.

  11. Ultrasound-assisted oxidative desulfurization and denitrogenation of liquid hydrocarbon fuels: A critical review.

    Science.gov (United States)

    Ja'fari, Mahsa; Ebrahimi, Seyedeh Leila; Khosravi-Nikou, Mohammad Reza

    2018-01-01

    Nowadays, a continuously worldwide concern for development of process to produce ultra-low sulfur and nitrogen fuels have been emerged. Typical hydrodesulfurization and hydrodenitrogenation technology deals with important difficulties such as high pressure and temperature operating condition, failure to treat some recalcitrant compounds and limitations to meet the stringent environmental regulations. In contrary an advanced oxidation process that is ultrasound assisted oxidative desulfurization and denitrogenation satisfies latest environmental regulations in much milder conditions with more efficiency. The present work deals with a comprehensive review on findings and development in the ultrasound assisted oxidative desulfurization and denitrogenation (UAOD) during the last decades. The role of individual parameters namely temperature, residence time, ultrasound power and frequency, pH, initial concentration and types of sulfur and nitrogen compounds on the efficiency are described. What's more another treatment properties that is role of phase transfer agent (PTA) and solvents of extraction step, reaction kinetics, mechanism of the ultrasound, fuel properties and recovery in UAOD are reviewed. Finally, the required future works to mature this technology are suggested. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    Energy Technology Data Exchange (ETDEWEB)

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  13. Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.

    Science.gov (United States)

    Yang, Bin; Ying, Guang-Guo; Zhang, Li-Juan; Zhou, Li-Jun; Liu, Shan; Fang, Yi-Xiang

    2011-03-01

    Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  15. Hydrocarbon isotope detection by elastic peak electron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kostanovskiy, I.A., E-mail: kostanovskiyia@gmail.com [National Research University MPEI, Krasnokazarmennaya 14, 111250 Moscow (Russian Federation); Afanas’ev, V.P. [National Research University MPEI, Krasnokazarmennaya 14, 111250 Moscow (Russian Federation); Naujoks, D. [Max-Planck-Institut für Plasmaphysik, Teilinstitut Greifswald, Wendelsteinstraße 1, D-17491 Greifswald (Germany); Mayer, M. [Max-Planck-Institut für Plasmaphysik, D-85748 Garching (Germany)

    2015-07-15

    Highlights: • PCVD hydrocarbon coatings containing protium or deuterium are analyzed via NRA, ERD, XPS and EPES. • EPES analysis with modern electron energy analyzer SPECS Phoibos 225 shows a clear signal from the hydrogen isotopes. • Different primary energies and scattering angles help to quantify isotope content from EPES spectra. - Abstract: Experimental results on the hydrocarbon isotope analysis by elastic peak electron spectroscopy are presented. Amorphous hydrocarbon samples (a-C:H, a-C:D) are prepared by PCVD and analyzed by nuclear reaction analysis (NRA), elastic recoil detection analysis (ERD), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES). Electron energy spectra show a clear signal from the hydrogen isotopes deuterium and protium. Different incident energies and scattering geometries help to resolve plasmon and elastic energy losses.

  16. Hydrocarbon isotope detection by elastic peak electron spectroscopy

    International Nuclear Information System (INIS)

    Kostanovskiy, I.A.; Afanas’ev, V.P.; Naujoks, D.; Mayer, M.

    2015-01-01

    Highlights: • PCVD hydrocarbon coatings containing protium or deuterium are analyzed via NRA, ERD, XPS and EPES. • EPES analysis with modern electron energy analyzer SPECS Phoibos 225 shows a clear signal from the hydrogen isotopes. • Different primary energies and scattering angles help to quantify isotope content from EPES spectra. - Abstract: Experimental results on the hydrocarbon isotope analysis by elastic peak electron spectroscopy are presented. Amorphous hydrocarbon samples (a-C:H, a-C:D) are prepared by PCVD and analyzed by nuclear reaction analysis (NRA), elastic recoil detection analysis (ERD), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES). Electron energy spectra show a clear signal from the hydrogen isotopes deuterium and protium. Different incident energies and scattering geometries help to resolve plasmon and elastic energy losses

  17. Heat-Activated Persulfate Oxidation of Chlorinated Solvents in Sandy Soil

    Directory of Open Access Journals (Sweden)

    Jialu Liu

    2014-01-01

    Full Text Available Heat-activated persulfate oxidative treatment of chlorinated organic solvents containing chlorinated ethenes and ethanes in soil was investigated with different persulfate dosages (20 g/L, 40 g/L, and 60 g/L and different temperatures (30°C, 40°C, and 50°C. Chlorinated organic solvents removal was increased as persulfate concentration increase. The persulfate dosage of 20 g/L with the highest OE (oxidant efficiency value was economically suitable for chlorinated organic solvents removal. The increasing temperature contributed to the increasing depletion of chlorinated organic solvents. Chlorinated ethenes were more easily removed than chlorinated ethanes. Moreover, the persulfate depletion followed the pseudo-first-order reaction kinetics (kps=0.0292 [PS]0+0.0008, R2=0.9771. Heat-activated persulfate appeared to be an effective oxidant for treatment of chlorinated hydrocarbons.

  18. Synthesis and characterization of cobalt-nichel oxides for the oxygen formation reaction

    International Nuclear Information System (INIS)

    Morales G, P.

    2001-01-01

    In this work the compounds of cobalt and nickel oxides and the mixtures of cobalt-nickel were prepared which were characterized and evaluated as electrocatalysts in the oxygen release reaction in alkaline media. The compounds were synthesised by the sol-gel method: heated at 400 and 500 Centigrade. The compounds characterization was realized by thermogravimetry, X-ray diffraction and Scanning electron microscopy. As the Co 3 O 4 and the Ni O as the mixtures Ni O/Co 3 O 4 were obtained as a porous material with a small particle size, characteristics which are presented by cause of the low temperature of synthesis. The electrocatalytic evaluation for the synthesised compounds for the oxygen release reaction was realized by cyclic volt amperometry in a 0.5M KOH solution. The oxides mixtures presented a well electrocatalytic activity to be used in the electrochemical release of oxygen. The current density and the electrochemically active area, in all the cases of mixtures is very higher to the Co 3 O 4 and Ni O ones. Observing with greater clearness the synergic effects, in the obtained mixture at 400 C. The oxides mixtures heated at 400 C were stables for the oxygen formation reaction. Therefore it is be able to say that the Ni O/Co 3 O 4 mixture counts on a great reactive area: electrocatalytic characteristic desirable to be a material used as anode in the electrolysis of water, which increases the oxygen release in the anode and so the hydrogen release in the cathode. (Author)

  19. Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

    Science.gov (United States)

    Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

    2015-11-04

    Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation.

  20. Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

    Science.gov (United States)

    2015-01-01

    Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

  1. Sources of polyaromatic hydrocarbons (PAH); Kildebestemmelse af polyaromatiske kulbrinter (PAH)

    Energy Technology Data Exchange (ETDEWEB)

    Egsgaard, H. [Forskningscenetr Risoe, Ald. for Plantebiologi og Biokemi (DK); Larsen, E. [Forskningscenter Risoe, Ald. for Optic og Fluid Dynamik (Denmark)

    2000-03-01

    Aromatic hydrocarbons including PAH compounds are thermally and chemically very stable compounds and are formed by gasification/pyrolysis of biomass. With reference to the tar compounds present in the produced gas from updraft gasifiers the sources responsible for the formation of naphthalene and poly-aromatic hydrocarbons have been investigated. The focus has been on thermal and oxidative conversions of compounds related to the lignin building blocks. Thus, phenols, 2-methoxy-phenols and 4-substituted-2-methoxy-phenols were investigated by introducing water solutions of the compounds into a continuos flow system operating in the temperature range 600-850 deg. C. The pyrolysis products were identified by GC/MS. The tar compounds reveal a well-defined and characteristic thermal transformation. Phenol is a strong source to naphthalene and indenes while 2-methoxyphenols are sources to aromatic oxo-compounds such as cinnamaldehyde. More complex systems are sources to higer PAH compounds. Thus, oligomers of phenol and 2-methoxyphenol give dibenzofuran and oligomers of isoeugenol are important sources to acenaphthylene. It is characteristic that the simple tar compounds investigated undergo loss of CO and hereby loss of the aromatic structure. The intermediary compounds are very reactive cyclo-pentadienes entering Diels-Alder reactions. The later products are transformed to aromatic compounds. The results may facilitate the determination of optimum conditions for updraft gasifiers and hence a reduction of PAH formation. (au)

  2. Caryophyllene driven diversity in an one-pot rearrangement of oxidation and transanular reactions

    Science.gov (United States)

    Tang, Hao-Yu; Quan, Lu-Lu; Yu, Jie; Zhang, Qiang; Gao, Jin-Ming

    2018-03-01

    Diversity oriented synthesis starting from natural products is a newly coming strategy to build diverse skeletons to meet the demands of high throughput screening in drug development. Caryophyllene was being considered as an ideal starting point to build divers natural-like sesquiterpenes due to its rich sources and build-in reactivity. In this paper, six new natural-like products (2-7) were synthesized form the natural cryophyllene oxide via cascade oxidation and transannular reactions in a one-pot procedure. Their structures were elucidated by exhaustive spectra method including 2D NMR and X-ray diffraction. Of the products, compounds 6 and 7 possess very similar skeleton to natural products. Our findings demonstrated that one-pot cascade reactions on macrocyclic natural products is a concise strategy to create diverse natural-like skeletons.

  3. Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

    Science.gov (United States)

    Marin, I. S.; Molson, J. W.

    2013-05-01

    Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

  4. Green chemistry perspectives of methane conversion via oxidative methylation of aromatics over zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Adebajo, M.O. [University of Queensland, St Lucia, Qld. (Australia)

    2007-06-15

    This paper provides a general overview of the recent work that we and other researchers have done on the utilisation of methane for catalytic methylation of aromatic compounds and for direct coal liquefaction for the production of liquid hydrocarbons. In particular, the paper presents a detailed description of more recent substantial experimental evidence that we have provided for the requirement of oxygen as a stoichiometry reactant for benzene methylation with methane over moderately acidic zeolite catalysts. The reaction, which has been termed 'oxidative methylation', was thus postulated to involve a two-step mechanism involving intermediate methanol formation by methane partial oxidation, followed by benzene methylation with methanol in the second step. However, strongly acidic zeolites can cause cracking of benzene to yield methylated products in the absence of oxygen. The participation of methane and oxygen, and the effective use of zeolite catalysts in this methylation reaction definitely have some positive green chemistry implications. Thus, the results of these previous studies are also discussed in this review in light of the principles and tools of green chemistry. Various metrics were used to evaluate the greenness, cost-effectiveness, and material and energy efficiency of the oxidative methylation reaction.

  5. The Role of Post Flame Oxidation on the UHC Emission for Combustion of Natural Gas and Hydrogen Containing fuels

    DEFF Research Database (Denmark)

    Jensen, Torben Kvist; Schramm, Jesper

    2003-01-01

    In-cylinder post flame oxidation of unburned hydro-carbons from crevices in a lean burn spark ignition engine has been examined for natural gas and mixtures of natural gas and a hydrogen containing producer gas. For this purpose a model was developed to describe the mixing of cold unburned...... during in-cylinder post oxidation. The Arrhenius parameters were determined using the reaction mechanism, which gave the prediction of the results from the combustion reactor experiments. The investigation showed that addition of producer gas to natural gas promotes the in-cylinder post oxidation...... significantly. Furthermore it was found that the cyclic variation in the post oxidation is reduced by addition of producer gas to natural gas....

  6. Evaluation of environmental samples containing heavy hydrocarbon components in environmental forensic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Raia, J.C.; Blakley, C.R.; Fuex, A.N.; Villalanti, D.C.; Fahrenthold, P.D. [Triton Anal Corp, Houston, TX (United States)

    2004-03-01

    This article presents a procedure to evaluate and characterize environmental samples containing mixtures of hydrocarbons over a wide boiling range of materials that include fuels and other products used in commerce. The range of the method extends to the higher boiling and heavier molecular weight hydrocarbon products in the range of motor oil, bunker fuel, and heavier residue materials. The procedure uses the analytical laboratory technique of high-temperature simulated distillation along with mathematical regression of the analytical data to estimate the relative contribution of individual products in mixtures of hydrocarbons present in environmental samples. An analytical technique to determine hydrocarbon-type distributions by gas chromatography-mass spectrometry with nitric oxide ionization spectrometry evaluation is also presented. This type of analysis allows complex hydrocarbon mixtures to be classified by their chemical composition, or types of hydrocarbons that include paraffins, cycloparaffins, monoaromatics, and polycyclic aromatic hydrocarbons. Characteristic hydrocarbon patterns for example, in the relative distribution of polycyclic aromatic hydrocarbons are valuable for determining the potential origin of materials present in environmental samples. These methods provide quantitative data for hydrocarbon components in mixtures as a function of boiling range and 'hydrocarbon fingerprints' of the types of materials present. This information is valuable in assessing environmental impacts of hydrocarbons at contaminated sites and establishing the liabilities and cost allocations for responsible parties.

  7. Monitoring biodegradation of hydrocarbons by stable isotope fractionation

    Science.gov (United States)

    Dorer, Conrad; Fischer, Anko; Herrmann, Steffi; Richnow, Hans-Hermann; Vogt, Carsten

    2010-05-01

    nitrate, sulfate or ferric iron as electron acceptor or using light as energy source [3,4,5]. Significantly different lambda values were also observed for the anaerobic degradation of xylenes initiated by the BSS [5]. The different lambda values obtained for the anaerobic degradation of toluene and xylenes might be caused by slightly different reaction mechanisms of BSS isoenzymes. In comparison, lambda and/or ɛbulk values for the methyl monohydroxylation of toluene with oxygen as co-substrate were significantly different for two tested strains each containing a different toluene attacking enzyme, indicating that specific enzymes for aerobic methyl group oxidation reactions can be detected by CSIA and 2D-CSIA. Our results show that the combined carbon and hydrogen isotope fractionation approach has great potential to elucidate biodegradation pathways of monoaromatic hydrocarbons in microcosm and field studies. Current work focus on (i) 2D-CSIA of aromatic and aliphatic hydrocarbons in degradation experiments using whole cells, and (ii) 2D-CSIA of aromatic hydrocarbons in in vitro experiments using cell extracts. [1] Fischer et al. (2008) Environ. Sci. Technol. 42, 4356-4363 [2] Mancini et al. (2008) Environ. Sci. Technol. 42, 8290-8296 [3] Vogt et al. (2008) Environ. Sci. Technol. 42, 7793-7800 [4] Tobler et al. (2008) Environ. Sci. Technol. 42, 7786-7792 [5] Herrmann et al. (2009) Environ. Microbiol. Reports 1, 535-544

  8. Electrode Kinetics and Gas Conversion in Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude

    The solid oxide fuel cell (SOFC) converts hydrogen, carbon monoxide and hydrocarbon fuels (directly) into electricity with very high efficiencies and has demonstrated almost comparable performance when operated in reverse mode as a solid oxide electrolysis cell (SOEC). In this case electrical (and...... thermal) energy is stored as chemical energy of reaction products. To this end, the cells are fed with steam (H2O electrolysis), carbon dioxide (CO2 electrolysis) or a mixture of both (H2O/CO2 co-electrolysis) and of course electrical (ΔG) and thermal (TΔS) energies for the splitting of reactant compounds...... of the solid oxide cell (SOC) and independent of polarization mode (fuel cell mode or electrolysis mode), the current flowing through the cell is limited by processes such as adsorption and desorption of reactants or products, diffusion through the porous electrodes, activation or charge transfer...

  9. Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

    Science.gov (United States)

    Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.; hide

    2013-01-01

    A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the

  10. Formalization of hydrocarbon conversion scheme of catalytic cracking for mathematical model development

    Science.gov (United States)

    Nazarova, G.; Ivashkina, E.; Ivanchina, E.; Kiseleva, S.; Stebeneva, V.

    2015-11-01

    The issue of improving the energy and resource efficiency of advanced petroleum processing can be solved by the development of adequate mathematical model based on physical and chemical regularities of process reactions with a high predictive potential in the advanced petroleum refining. In this work, the development of formalized hydrocarbon conversion scheme of catalytic cracking was performed using thermodynamic parameters of reaction defined by the Density Functional Theory. The list of reaction was compiled according to the results of feedstock structural-group composition definition, which was done by the n-d-m-method, the Hazelvuda method, qualitative composition of feedstock defined by gas chromatography-mass spectrometry and individual composition of catalytic cracking gasoline fraction. Formalized hydrocarbon conversion scheme of catalytic cracking will become the basis for the development of the catalytic cracking kinetic model.

  11. Chain chemical reactions during matrix devitrification

    International Nuclear Information System (INIS)

    Barkalov, I.M.

    1980-01-01

    Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

  12. Fenton's reagent as a remediation process in water treatment: application to the degradation of polycyclic aromatic hydrocarbons in waters and sewage sludges; La reaction de fenton comme procede de rehabilitation dans le traitement des eaux: application a la degradation des hydrocarbures aromatiques polycycliques dans les eaux et les boues residuaires

    Energy Technology Data Exchange (ETDEWEB)

    Flotron, V.

    2004-05-15

    This study is related to the application of Fenton's reagent to remedy matrices contaminated by polycyclic aromatic hydrocarbons (PAHs). In aqueous solution, the choice of the reagent implementation is important, in order to generate enough radicals to oxidize pollutants. Degradation of the organic compounds is possible, but a large difference in reactivity is observed between 'alternant' and 'non-alternant' PAHs (with a five carbon atoms cycle). Besides, if a few specific precautions are omitted, the PAHs can sorb onto the flask inside surface, and therefore not undergo oxidation. The results on sewage sludges show that under certain conditions (high reagent concentrations), the pollutants can be oxidised although they are adsorbed. Moreover, it appears that the matrix itself plays an important role, as the iron oxides seem to be able to decompose hydrogen peroxide, and thus initiate Fenton reaction. Its application to contaminated soils and sediments is also possible. (author)

  13. Optimization of reaction parameters for the electrochemical oxidation of lidocaine with a Design of Experiments approach

    NARCIS (Netherlands)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar

    2015-01-01

    Identification of potentially toxic oxidative drug metabolites is a crucial step in the development of new drugs. Electrochemical methods are useful to study oxidative drug metabolism, but are not widely used to synthesize metabolites for follow-up studies. Careful optimization of reaction

  14. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  15. Coupling of separation and reaction in zeolite membrane reactor for hydroisomerization of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gora, L.; Jansen, J.C. [Ceramic Membrane Centre, The Pore, DelftChemTech, Delft Univ. of Technology, Delft (Netherlands)

    2005-03-01

    A zeolite membrane reactor has been developed for the hydroisomerization of hydrocarbons, in which the linear molecules are separated from branched ones on the silicalite-1 membrane prior to conversion of the permeated linear hydrocarbons to equilibrium levels on the catalyst bed. Model studies using C{sub 6} components are conducted. n-C{sub 6} separated from 2MP (selectivity 24) is converted for 72% with 36% selectivity towards di-branched isomers (at 393 K). The results indicate that platinum containing chlorinated alumina/silicalite-1 membrane reactor has a potential in upgrading octane values and offers advantages such as higher efficiency, better process control and lower consumption of energy. (orig.)

  16. Coupling of separation and reaction in zeolite membrane reactor for hydroisomerization of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gora, L.; Maloncy, M.L.; Jansen, J.C. [Ceramic Membrane Centre, The Pore, DelftChemTech, Delft Univ. of Technology (Netherlands)

    2004-07-01

    A zeolite membrane reactor has been developed for the hydroisomerization of hydrocarbons, in which the linear molecules are separated from branch ones on the silicalite-1 membrane prior to conversion of the permeated linear hydrocarbons to equilibrium levels on the catalyst bed. A model studies using C6 components are conduct. Separated n-C6 from 2MP (selectivity 24) is converted for 72% with 36% selectivity towards di-branched isomers (at 393 K). The results indicate that platinum containing chlorinated alumina/silicalite-1 membrane reactor has a potential in upgrading octane values and offers advantages such as higher efficiency, better process control and lower consumption of energy. (orig.)

  17. Ozone and the oxidizing properties of the troposphere

    International Nuclear Information System (INIS)

    Megie, G.

    1996-01-01

    This article is about the rising concentration of ozone and photo-oxidizers observed in the troposphere, the atmosphere between the ground and a height of 10 to 15 km. This serious global environmental problem has up to now been less well known than the greenhouse effect or the decrease in stratospheric ozone. This is because it varies with time and place and involves many complicated physico-chemical and atmospheric processes. At our latitudes, the average ozone concentration in the air we breathe has quadrupled since the beginning of this century. In polluted areas it often exceeds the recommended norms. This increase in ozone concentrations in the lower atmosphere directly reflects the impact of man-made emissions of compounds like methane, carbon monoxide, hydrocarbons and nitrogen oxides. Sunlight acts on these compounds to form ozone via complicated chemical reactions. This change in oxidizing properties of the troposphere is beginning produce perceptible effects on vegetable production, human health and climate. (author). 24 refs., 5 figs., 4 tabs

  18. Metabolic activation of polycyclic and heterocyclic aromatic hydrocarbons and DNA damage: A review

    International Nuclear Information System (INIS)

    Xue Weiling; Warshawsky, David

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic compounds (HACs) constitute a major class of chemical carcinogens present in the environment. These compounds require activation to electrophilic metabolites to exert their mutagenic or carcinogenic effects. There are three principal pathways currently proposed for metabolic activation of PAH and HAC: the pathway via bay region dihydrodiol epoxide by cytochrome P450 enzymes (CYPs), the pathway via radical cation by one-electron oxidation, and the ortho-quinone pathway by dihydrodiol dehydrogenase (DD). In addition to these major pathways, a brief description of a minor metabolic activation pathway, sulfonation, for PAHs that contain a primary benzylic alcoholic group or secondary hydroxyl group(s) is included in this review. The DNA damages caused through the reactive metabolites of PAH/HAC are described involving the DNA covalent binding to form stable or depurinating adducts, the formation of apurinic sites, and the oxidative damage. The review emphasizes the chemical/biochemical reactions involved in the metabolic processes and the chemical structures of metabolites and DNA adducts

  19. Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.

    2014-01-01

    was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature......The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40°C) for 28 or 42 days. The oxidative stability of krill oil...

  20. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  1. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    Science.gov (United States)

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

  2. Aryl hydrocarbon receptor protects lung adenocarcinoma cells against cigarette sidestream smoke particulates-induced oxidative stress

    International Nuclear Information System (INIS)

    Cheng, Ya-Hsin; Huang, Su-Chin; Lin, Chun-Ju; Cheng, Li-Chuan; Li, Lih-Ann

    2012-01-01

    Environmental cigarette smoke has been suggested to promote lung adenocarcinoma progression through aryl hydrocarbon receptor (AhR)-signaled metabolism. However, whether AhR facilitates metabolic activation or detoxification in exposed adenocarcinoma cells remains ambiguous. To address this question, we have modified the expression level of AhR in two human lung adenocarcinoma cell lines and examined their response to an extract of cigarette sidestream smoke particulates (CSSP). We found that overexpression of AhR in the CL1-5 cell line reduced CSSP-induced ROS production and oxidative DNA damage, whereas knockdown of AhR expression increased ROS level in CSSP-exposed H1355 cells. Oxidative stress sensor Nrf2 and its target gene NQO1 were insensitive to AhR expression level and CSSP treatment in human lung adenocarcinoma cells. In contrast, induction of AhR expression concurrently increased mRNA expression of xenobiotic-metabolizing genes CYP1B1, UGT1A8, and UGT1A10 in a ligand-independent manner. It appeared that AhR accelerated xenobiotic clearing and diminished associated oxidative stress by coordinate regulation of a set of phase I and II metabolizing genes. However, the AhR-signaled protection could not shield cells from constant oxidative stress. Prolonged exposure to high concentrations of CSSP induced G0/G1 cell cycle arrest via the p53–p21–Rb1 signaling pathway. Despite no effect on DNA repair rate, AhR facilitated the recovery of cells from growth arrest when CSSP exposure ended. AhR-overexpressing lung adenocarcinoma cells exhibited an increased anchorage-dependent and independent proliferation when recovery from exposure. In summary, our data demonstrated that AhR protected lung adenocarcinoma cells against CSSP-induced oxidative stress and promoted post-exposure clonogenicity. -- Highlights: ► AhR expression level influences cigarette sidestream smoke-induced ROS production. ► AhR reduces oxidative stress by coordinate regulation of

  3. Aryl hydrocarbon receptor protects lung adenocarcinoma cells against cigarette sidestream smoke particulates-induced oxidative stress

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Ya-Hsin [Graduate Institute of Basic Medical Science, School of Medicine, China Medical University, Taichung 40402, Taiwan, ROC (China); Huang, Su-Chin; Lin, Chun-Ju; Cheng, Li-Chuan [Division of Environmental Health and Occupational Medicine, National Health Research Institutes, Zhunan, Miaoli 35053, Taiwan, ROC (China); Li, Lih-Ann, E-mail: lihann@nhri.org.tw [Division of Environmental Health and Occupational Medicine, National Health Research Institutes, Zhunan, Miaoli 35053, Taiwan, ROC (China)

    2012-03-15

    Environmental cigarette smoke has been suggested to promote lung adenocarcinoma progression through aryl hydrocarbon receptor (AhR)-signaled metabolism. However, whether AhR facilitates metabolic activation or detoxification in exposed adenocarcinoma cells remains ambiguous. To address this question, we have modified the expression level of AhR in two human lung adenocarcinoma cell lines and examined their response to an extract of cigarette sidestream smoke particulates (CSSP). We found that overexpression of AhR in the CL1-5 cell line reduced CSSP-induced ROS production and oxidative DNA damage, whereas knockdown of AhR expression increased ROS level in CSSP-exposed H1355 cells. Oxidative stress sensor Nrf2 and its target gene NQO1 were insensitive to AhR expression level and CSSP treatment in human lung adenocarcinoma cells. In contrast, induction of AhR expression concurrently increased mRNA expression of xenobiotic-metabolizing genes CYP1B1, UGT1A8, and UGT1A10 in a ligand-independent manner. It appeared that AhR accelerated xenobiotic clearing and diminished associated oxidative stress by coordinate regulation of a set of phase I and II metabolizing genes. However, the AhR-signaled protection could not shield cells from constant oxidative stress. Prolonged exposure to high concentrations of CSSP induced G0/G1 cell cycle arrest via the p53–p21–Rb1 signaling pathway. Despite no effect on DNA repair rate, AhR facilitated the recovery of cells from growth arrest when CSSP exposure ended. AhR-overexpressing lung adenocarcinoma cells exhibited an increased anchorage-dependent and independent proliferation when recovery from exposure. In summary, our data demonstrated that AhR protected lung adenocarcinoma cells against CSSP-induced oxidative stress and promoted post-exposure clonogenicity. -- Highlights: ► AhR expression level influences cigarette sidestream smoke-induced ROS production. ► AhR reduces oxidative stress by coordinate regulation of

  4. Producing light hydrocarbons by destructive hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Fohlen, J H

    1928-06-20

    A method of obtaining light hydrocarbons from fuels and natural or industrial carbonaceous materials by cracking under pressure from 5 to 200 atmospheres and within a temperature range of 200 to 1,000/sup 0/C, the cracking operation being assisted by the presence of catalysts such as metallic halides, simultaneously, with hydrogenation by means of nascent hydrogen in the reaction chamber.

  5. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  6. Effect of low-temperature oxidation on the pyrolysis and combustion of whole oil

    International Nuclear Information System (INIS)

    Murugan, Pulikesi; Mahinpey, Nader; Mani, Thilakavathi; Asghari, Koorosh

    2010-01-01

    Low-temperature oxidation (LTO) of the Fosterton crude oil mixed with its reservoir sand has been investigated in a tubular reactor. Reservoir sand saturated with 15 wt% of crude oil (20.5 o API gravity) was subjected to air injection at low-temperature (220 o C) for a period of time (17 h and 30 min), resulting in the formation of an oxygenated hydrocarbon fuel. The vent gases were analyzed for the content of CO, CO 2 , and oxygen and the residue was analyzed to determine the elemental composition and calorific value. The presence of LTO region was verified from the values of apparent H/C ratio. In addition, thermal behavior and combustion kinetics of the residue was investigated using thermogravimetric analysis (TGA). TG involves both non-isothermal and isothermal analysis and kinetic data was derived from isothermal studies. The general model for nth order reaction was used to obtain the kinetic parameters of the coke oxidation reaction. The activation energy, frequency factor and order of the reactions were determined using the model.

  7. Positive patch test reactions to oxidized limonene: exposure and relevance.

    Science.gov (United States)

    Bråred Christensson, Johanna; Andersen, Klaus E; Bruze, Magnus; Johansen, Jeanne D; Garcia-Bravo, Begoña; Gimenez Arnau, Ana; Goh, Chee-Leok; Nixon, Rosemary; White, Ian R

    2014-11-01

    R-Limonene is a common fragrance terpene found in domestic and industrial products. R-Limonene autoxidizes on air exposure, and the oxidation products can cause contact allergy. In a recent multicentre study, 5.2% (range 2.3-12.1%) of 2900 patients showed a positive patch test reaction to oxidized R-limonene. To study the exposure to limonene among consecutive dermatitis patients reacting to oxidized R-limonene in an international setting, and to assess the relevance of the exposure for the patients' dermatitis. Oxidized R-limonene 3.0% (containing limonene hydroperoxides at 0.33%) in petrolatum was tested in 2900 consecutive dermatitis patients in Australia, Denmark, the United Kingdom, Singapore, Spain, and Sweden. A questionnaire assessing exposure to limonene-containing products was completed. Overall, exposure to products containing limonene was found and assessed as being probably relevant for the patients' dermatitis in 36% of the limonene-allergic patients. In Barcelona and Copenhagen, > 70% of the patients were judged to have had an exposure to limonene assessed as relevant. Oxidized R-limonene is a common fragrance allergen, and limonene was frequently found in the labelling on the patients' products, and assessed as relevant for the patients' dermatitis. A large number of domestic and occupational sources for contact with R-limonene were identified. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  8. Automatic reduction of the hydrocarbon reaction mechanisms in fusion edge plasmas

    International Nuclear Information System (INIS)

    Dauwe, A.; Tytgadt, M.; Reiter, D.; Baelmans, M.

    2006-11-01

    For predictions of the tritium inventory in future fusion devices like ITER, the amount of eroded carbon and the hydrogen concentrations in co-deposited hydrocarbon layers have to be predicted quantitatively. Predictions about the locations of co-deposited layers are also necessary in order to design deposition diagnostics and layer removal methods. This requires a detailed physical understanding of the erosion and carbon migration processes, and computer simulations. For accurate simulation the multi-species code EIRENE would require to include over 50 participating species. Because such a calculation is computationally prohibitive current codes are being reduced, typically in an ad hoc fashion. In this work the potential of the mathematically sound method of intrinsic low dimensional manifolds (ILDM) for computational speed-up of the hydrocarbon transport problem simulation is thoroughly investigated. It is basically the Monte Carlo implementation of EIRENE that makes this task so challenging. As the method can substantially ameliorate the results in comparison to the conventional reduction mechanisms a step towards ILDM-reduced kinetics is conceived and tested. (orig.)

  9. Evaluation of the kinetic oxidation of aqueous volatile organic compounds by permanganate.

    Science.gov (United States)

    Mahmoodlu, Mojtaba G; Hassanizadeh, S Majid; Hartog, Niels

    2014-07-01

    The use of permanganate solutions for in-situ chemical oxidation (ISCO) is a well-established groundwater remediation technology, particularly for targeting chlorinated ethenes. The kinetics of oxidation reactions is an important ISCO remediation design aspect that affects the efficiency and oxidant persistence. The overall rate of the ISCO reaction between oxidant and contaminant is typically described using a second-order kinetic model while the second-order rate constant is determined experimentally by means of a pseudo first order approach. However, earlier studies of chlorinated hydrocarbons have yielded a wide range of values for the second-order rate constants. Also, there is limited insight in the kinetics of permanganate reactions with fuel-derived groundwater contaminants such as toluene and ethanol. In this study, batch experiments were carried out to investigate and compare the oxidation kinetics of aqueous trichloroethylene (TCE), ethanol, and toluene in an aqueous potassium permanganate solution. The overall second-order rate constants were determined directly by fitting a second-order model to the data, instead of typically using the pseudo-first-order approach. The second-order reaction rate constants (M(-1) s(-1)) for TCE, toluene, and ethanol were 8.0×10(-1), 2.5×10(-4), and 6.5×10(-4), respectively. Results showed that the inappropriate use of the pseudo-first-order approach in several previous studies produced biased estimates of the second-order rate constants. In our study, this error was expressed as a function of the extent (P/N) in which the reactant concentrations deviated from the stoichiometric ratio of each oxidation reaction. The error associated with the inappropriate use of the pseudo-first-order approach is negatively correlated with the P/N ratio and reached up to 25% of the estimated second-order rate constant in some previous studies of TCE oxidation. Based on our results, a similar relation is valid for the other volatile

  10. Characterization of electro-oxidation catalysts using scanning electrochemical and mass spectral methods

    Science.gov (United States)

    Jambunathan, Krishnakumar

    Low temperature fuel cells have many potential benefits, including high efficiency, high energy density and environmental friendliness. However, logistically appealing fuels for this system, such as reformed hydrocarbons or alcohols, exhibit poor performance because of catalyst poisoning that occurs during oxidation at the anode. This research focuses on the analysis of several model fuels and catalyst materials to understand the impact of catalyst poisoning on reactivity. Two novel experimental tools were developed based upon the local measurement of catalyst performance using scanning, reactivity mapping probes. The Scanning Electrochemical Microscope (SECM) was used to directly measure the rate constant for hydrogen oxidation in the presence and absence of dissolved CO. The Scanning Differential Electrochemical Mass Spectrometer (SDEMS) was exploited to measure the partial and complete oxidation products of methanol and ethanol oxidation. The reactivity of Pt and Pt/Ru catalysts towards the hydrogen oxidation reaction in the absence and presence of adsorbed CO was elucidated using the SECM. Steady state rate constant measurements in the absence of CO showed that the rate of hydrogen oxidation reaction exceeded 1 cms-1 . Steady state rate constant measurements in the presence of CO indicated that the platinum surface is completely inactive due to adsorbed CO. Addition of as little as 6% Ru to the Pt electrode was found to significantly improve the activity of the electrode towards CO removal. SDEMS was used to study the electro-oxidation of methanol on Pt xRuy electrodes at different electrode potentials and temperatures. Screening measurements performed with the SDEMS showed that PtxRu y electrodes containing 6--40% Ru had the highest activity for methanol oxidation. Current efficiencies for CO2 were also calculated under different conditions. SDEMS was also used to study the electro-oxidation of ethanol on Pt xRuy electrodes. The reaction was found to occur

  11. A case study of the intrinsic bioremediation of petroleum hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barker, G.W.; Raterman, K.T.; Fisher, J.B.; Corgan, J.M. [and others

    1995-12-31

    Condensate liquids have been found to contaminate soil and groundwater at two gas production sites in the Denver Basin operated by Amoco Production Co. These sites have been closely monitored since July 1993 to determine whether intrinsic aerobic or anaerobic bioremediation of hydrocarbons occurs at a sufficient rate and to an adequate endpoint to support a no-intervention decision. Groundwater monitoring and analysis of soil cores suggest that intrinsic bioremediation is occurring at these sites by multiple pathways including aerobic oxidation, Fe{sup 3+} reduction, and sulfate reduction. In laboratory experiments the addition of gas condensate hydrocarbons to saturated soil from the gas production site stimulated sulfate reduction under anaerobic and oxygen-limiting conditions, and nitrate and Fe{sup 3+} reduction under oxygen-limiting conditions, compared to biotic controls that lacked hydrocarbon and sterile controls. The sulfate reduction corresponded to a reduction in the amount of toluene relative to other hydrocarbons. These results confirmed that subsurface soils at the gas production site have the potential for intrinsic bioremediation of hydrocarbons.

  12. Hydrogen incorporation and radiation induced dynamics in metal-oxide-silicon structures. A study using nuclear reaction analysis

    International Nuclear Information System (INIS)

    Briere, M.A.

    1993-07-01

    Resonant nuclear reaction analysis, using the 1 H( 15 N, αγ) 12 C reaction at 6.4 MeV, has been successfully applied to the investigation of hydrogen incorporation and radiation induced migration in metal-oxide-silicon structures. A preliminary study of the influence of processing parameters on the H content of thermal oxides, with and without gate material present, has been performed. It is found that the dominant source of hydrogen in Al gate devices and dry oxides is often contamination, likely in the form of adsorbed water vapor, formed upon exposure to room air after removal from the oxidation furnace. Concentrations of hydrogen in the bulk oxide as high as 3 10 20 cm -3 (Al gate), and as low as 1 10 18 cm -3 (poly Si-gate) have been observed. Hydrogen accumulation at the Si-SiO 2 interface has been reproducibly demonstrated for as-oxidized samples, as well as for oxides exposed to H 2 containing atmospheres during subsequent thermal processing. The migration of hydrogen, from the bulk oxide to the silicon-oxide interface during NRA, has been observed and intensively investigated. A direct correlation between the hydrogen content of the bulk oxide and the radiation generated oxide charges and interface states is presented. These data provide strong support for the important role of hydrogen in determining the radiation sensitivity of electronic devices. (orig.)

  13. The catalytic oxidation of organic contaminants in a packed bed reactor

    NARCIS (Netherlands)

    van de Beld, L.; Bijl, M.P.G.; Reinders, A.; van der Wert, B.; Westerterp, K.R.

    1994-01-01

    The catalytic oxidation of several hydrocarbons was studied over noble metal and metal oxide catalysts. A fast empirical method was developed to determine the minimum operating temperature required to guarantee complete conversion of the hydrocarbon. The influence of the operating parameters such as

  14. Emissions of hydrocarbons from marine phytoplankton—Some results from controlled laboratory experiments

    Science.gov (United States)

    McKay, W. A.; Turner, M. F.; Jones, B. M. R.; Halliwell, C. M.

    Laboratory experiments have been carried out to help assess and quantify the role of marine phytoplankton in the production of non-methane hydrocarbons. Evidence is presented here that supports the hypothesis that some short-chain hydrocarbons are produced during diatom and dinoflagellate lifecycles. The pattern of their emissions to the air above axenic unicultures of diatoms and dinoflagellates has been followed. The results suggest that ethane, ethene, propane and propene are produced during the autolysis of some phytoplankton, possibly by the oxidation of polyunsaturated lipids released into their culture medium. In contrast, isoprene and hexane appear during phytoplankton growth and are thus most likely produced either directly by the plankton or through the oxidation of exuded dissolved organic carbon.

  15. Improved reaction sintered silicon nitride. [protective coatings to improve oxidation resistance

    Science.gov (United States)

    Baumgartner, H. R.

    1978-01-01

    Processing treatments were applied to as-nitrided reaction sintered silicon nitride (RSSN) with the purposes of improving strength after processing to above 350 MN/m2 and improving strength after oxidation exposure. The experimental approaches are divided into three broad classifications: sintering of surface-applied powders; impregnation of solution followed by further thermal processing; and infiltration of molten silicon and subsequent carburization or nitridation of the silicon. The impregnation of RSSN with solutions of aluminum nitrate and zirconyl chloride, followed by heating at 1400-1500 C in a nitrogen atmosphere containing silicon monoxide, improved RSSN strength and oxidation resistance. The room temperature bend strength of RSSN was increased nearly fifty percent above the untreated strength with mean absolute strengths up to 420 MN/m2. Strengths of treated samples that were measured after a 12 hour oxidation exposure in air were up to 90 percent of the original as-nitrided strength, as compared to retained strengths in the range of 35 to 60 percent for untreated RSSN after the same oxidation exposure.

  16. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    Science.gov (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  17. Method for thermal recovery of hydrocarbons from an underground formation

    Energy Technology Data Exchange (ETDEWEB)

    1962-11-13

    In a thermal recovery procedure for hydrocarbons from an underground formation, an oxygen-containing gas is injected through at least one input well into the formation. A part of the hydrocarbons in the formation is then ignited and an oxidation front is created. This front moves under the influence of the injected gas to at least one production well in the formation. The temperature in the burning front is higher than approximately 200/sup 0/C but lower than approximately 350/sup 0/C. (4 claims)

  18. Gamma irradiation of hydrocarbon-liquid nitrogen systems and the synthesis of ammonia

    International Nuclear Information System (INIS)

    Fleming, H.L.

    1982-01-01

    The 60 Co-gamma radiolysis of hydrocarbons (HC)-liquid N 2 mixtures at 77 0 K and 1.8 atm of pressure was investigated. Batch irradiation studies of methane, ethane, and ethylene and semibatch studies of methane were made in the presence and absence of transition metal oxide catalysts. In noncatalyzed systems, the effects of varying the radiation dose, total dose, solute feed rate and concentration and liquid N 2 volume were investigated. NH 3 was found to be the major N-containing product in the alkane solute system. N 2 and HC radical addition was found to be the predominate initial reaction for nitrogeneous product formation. Results of scavenger studies indicate that excited N 2 played a lesser role in precursor formation. All product yields were found to be dependent upon the H-containing species availability in the liquid N 2 solution. Production rates were limited by HC solubility. The use of the transition metal oxide supported catalyst greatly increased product formation in all systems. Product yields were found to be dependent upon the available catalyst surface area, metal loading, and reduction techniques for each metal examined. As evidenced by the radiation lag time studies, the stability of the N 2 precursors on the catalyst surface was believed to be a significant factor in reaction enhancement. Energy transfer from the catalyst to the absorbates was examined and could not be ruled out

  19. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  20. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-01-01

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

  1. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  2. Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

    Directory of Open Access Journals (Sweden)

    David R. Sellick

    2015-04-01

    Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

  3. The oxidative response and viable reaction mechanism of the textile dyes by fenton reagent

    International Nuclear Information System (INIS)

    Masooda, Q.; Hijira, T.; Sitara, M.; Sehar, M.; Sundus, A.; Mohsin, A.

    2017-01-01

    The mechanism of the degradation of the Reactive Red 239 and Reactive Blue 19 by Fenton reagent was studied by advanced oxidation process in aqueous medium. The spectroscopic technique was adopted for the measurements of dye concentration. Moreover they were determined at 540 nm and 590 nm, respectively. Kinetics of the reaction was studied under the effect of concentration of reactive dyes, concentration of oxidant were followed under pseudo first order condition and found to influence the catalytic mechanism. The pH of the medium, vibrant response of several cations and anions and influence of ionic strength on the reaction kinetics were also monitored. Physical evidences for the degradation and mineralization of the dyes were evaluated by Lime water test, Ring Test and TLC test also confirmed the degradation of dye. Inhibitory effects of dyes were observed by CO3-, HCO3-, HPO42-, Cl-, I- Al3+ and Na+. Thermodynamic activation parameters in the oxidation reaction were studied and mode of mechanism was suggested on the basic of these parameters. This study explored the safe and eco friendly degradation of the textile dyes under Pseudo first order rate constant. It was observed that Fenton assisted degradation of the dyes under controlled conditions was found to be favorable for the treatment of textile wastewater. Moreover compared to other chemical methods it is effective and harmless to the environment. (author)

  4. Fischer-Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    A.R. de la Osa; A. De Lucas; A. Romero; J.L. Valverde; P. Sanchez [University of Castilla-La Mancha, Ciudad Real (Spain). Chemical Engineering Department

    2011-05-15

    The effects of reaction conditions on the Fischer-Tropsch activity and product distribution of an alkali-earth metal promoted cobalt based catalyst were studied. The influence of the promoter on the reducibility and cobalt particle size was studied by different techniques, including N{sub 2} adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption and acid-base titrations. Experiments were carried out on a bench-scale fixed bed reactor and catalysts were prepared by incipient wetness impregnation. It was observed that addition of a small amount of calcium oxide as a promoter (0.6 wt.%) improved the cobalt oxide reducibility and reduced the formation of cobalt-aluminate species. A positive correlation between basicity and particle size was observed. In terms of FTS results, CO conversion and C{sub 5}{sup +} selectivity were found to be enhanced by the addition of this promoter. It was important to note that the addition of calcium shifted the distribution to mainly C{sub 16}-C{sub 18} hydrocarbons fraction, which could be greatly considered for a diesel formulation. Furthermore, the variation of the reaction conditions seemed to influence product distribution in a lesser extent than unpromoted catalyst. Also, a displacement of hydrocarbon distribution to higher molecular weight with decreasing space velocity and temperature was observed. Moreover, the addition of calcium to the cobalt based catalyst was found to greatly maintain selectivity to C{sub 5}{sup +} for a wide range of H{sub 2}/CO molar ratios. 60 refs., 10 figs., 5 tabs.

  5. Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

    International Nuclear Information System (INIS)

    Akulov, G.P.; Korsakova, N.A.

    1992-01-01

    Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

  6. Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

    Science.gov (United States)

    Jang, Seongwan; Yoon, Chohye; Lee, Jae Myung; Park, Sungkyun; Park, Kang Hyun

    2016-11-02

    HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di- tert -butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.

  7. High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Scott, Lawrence T. [Boston College, Chestnut Hill, MA (United States). Merkert Chemistry Center, Dept. of Chemistry

    2017-05-15

    The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figure prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion

  8. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

    2016-08-05

    Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

  9. The oxidative burst reaction in mammalian cells depends on gravity

    OpenAIRE

    Adrian, A; Schoppmann, K; Sromicki, J; Brungs, S; von der Wiesche, M; Hock, B; Kolanus, W; Hemmersbach, R; Ullrich, O

    2013-01-01

    Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to...

  10. Thermally promoted addition of undecylenic acid on thermally hydrocarbonized porous silicon optical reflectors

    OpenAIRE

    Jalkanen, Tero; Mäkilä, Ermei; Sakka, Tetsuo; Salonen, Jarno; Ogata, Yukio H

    2012-01-01

    Thermally promoted addition of undecylenic acid is studied as a method for modifying porous silicon optical reflectors that have been pre-treated with thermal hydrocarbonization. Successful derivatization of undecylenic acid is demonstrated and confirmed with Fourier transform infrared and X-ray photoelectron spectroscopies. The results indicate that the hydrocarbonization pre-treatment considerably improves stability against oxidation and chemical dissolution in basic environments. The two-s...

  11. Adsorption of Polycyclic aromatic hydrocarbons (fluoranthene and anthracenemethanol) by functional graphene oxide and removal by pH and temperature-sensitive coagulation.

    Science.gov (United States)

    Zhang, Caili; Wu, Lin; Cai, Dongqing; Zhang, Caiyun; Wang, Ning; Zhang, Jing; Wu, Zhengyan

    2013-06-12

    A new kind of functional graphene oxide with fine stability in water was fabricated by mixing graphene oxide (GO) and brilliant blue (BB) with a certain weight ratio. The adsorption performance of this mixture of BB and GO (BBGO) to polycyclic aromatic hydrocarbons (anthracenemethanol (AC) and fluoranthene (FL)) was investigated, and the results indicated BBGO possessed adsorption capacity of 1.676 mmol/g and removal efficiency of 72.7% as to AC and adsorption capacity of 2.212 mmol/g and removal efficiency of 93.2% as to FL. After adsorption, pH and temperature-sensitive coagulation (PTC) method was used to remove the AC/BBGO or FL/BBGO complex and proved to be an effective approach to flocculate the AC/BBGO or FL/BBGO complex into large flocs, which tended to be removed from the aqueous solution.

  12. Comparative study of radical oxidation of DNA and its nucleosides by hydroxyl radicals and ferryl ions generated by the Fenton reaction

    International Nuclear Information System (INIS)

    Mouret, J.F.; Berger, M.; Anselmino, C.; Polverelli, M.; Cadet, J.

    1991-01-01

    A comparative study of the reaction of hydroxyl radicals and Fenton type oxidative species with DNA and 2'-deoxyribonucleosides was investigated. This study was based on the characterization of the diamagnetic products resulting from the chemical transformation of the transient radicals. Emphasis was placed on the radical oxidative reactions of the purine nucleosides. It is interesting to note that oxidative purine radicals can be reduced by reagents such as ascorbic acid or N,N,N',N'-tetramethyl-1, 4-p-phenylenediamine. The observed differences in the nature of the decomposition products resulting from the Fenton reaction are not consistent with the nature of the oxidative species (hydroxyl radicals or ferryl ions) involved, but due to the presence of ferrous sulfate [fr

  13. On-line probe for fast electrochemistry/electrospray mass spectrometry. Investigation of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Xu, X; Lu, W; Cole, R B

    1996-12-01

    A newly invented probe accessory for fast electrochemistry/electrospray mass spectrometry (EC/ESMS) is presented and evaluated. The device features a low-volume, three-electrode electrochemical cell which has been designed with a minimum distance between the working electrode and the "Taylor cone" inherent to the electrospray process. This configuration limits the time between electrochemical generation of ions and mass spectrometric analysis to an absolute minimum. A fused-silica layer insulates the microcylinder working electrode from the sample solution until immediately prior to the electrospray region, postponing electrode processes until the last moment. The same fused-silica layer insulates the working electrode from the surrounding auxiliary electrode, a stainless steel capillary that also serves as the electrospray capillary. The performance and capabilities of the novel electrochemistry/electrospray mass spectrometry system have been evaluated using polycyclic aromatic hydrocarbons (PAHs) as test analytes. In the positive ion EC/ESMS mode, oxidized forms (one-electron removal) of PAHs are produced in high yield. The ability to analyze reaction products appearing subsequent to the initial oxidation is also demonstrated.

  14. The sixth international congress on toxic combustion byproducts. Technical program and abstract book

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-07-01

    Topics of this proceedings volume are: technical approaches - waste treatment; general toxicology of combustion byproducts; reaction mechanisms (e.g. formation and decomposition of hydrocarbons and chlorinated hydrocarbons, nitrogen oxides); thermal treatment - reactionas at low temperatures; heterogeneous reactions - heterogeneous systems. (SR)

  15. RuO4-mediated oxidation of secondary amines 2. imines as main reaction intermediates

    Directory of Open Access Journals (Sweden)

    Florea Cristina A.

    2017-01-01

    Full Text Available Oxidation by RuO4 (generated in situ from RuO2 and NaIO4 of secondary amines such as Bn–NH–CH2R (1; R=H, Me gave complex reaction mixtures, but mainly amides. In the presence of cyanide, the leading products were α-aminonitriles. Comparison of the oxidation products of 1 with those from the corresponding imines PhCH=N–CH2R and Bn–N=CH–R showed that formation of the indicated imines is the first main step in the oxidation of 1. A detailed mechanism is proposed.

  16. Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

    Science.gov (United States)

    Merino-Garcia, I.; Albo, J.; Irabien, A.

    2018-01-01

    Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

  17. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  18. Effect of oxidation on the chemical nature and distribution of low-temperature pyrolysis products from bituminous coal

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.; MacPhee, J.A.; Vancea, L.; Ciavaglia, L.A.; Nandi, B.N.

    1983-04-01

    Two bituminous coals, a high volatile Eastern Canadian and a medium volatile Western Canadian, were used to investigate the effect of oxidation on yields and chemical composition of gases, liquids and chars produced during coal pyrolysis. Pyrolysis experiments were performed at 500 C using the Fischer assay method. Mild oxidation of coals resulted in a decrease of liquid hydrocarbon yields. Further coal oxidation increased the proportion of aromatic carbon in liquid products as determined by N.M.R. and also increased the content of oxygen in liquid products. The content of oxygen in chars was markedly lower than in corresponding coals. An attempt is made to explain reactions occurring during oxidation and subsequent pyrolysis of coal on the basis of differences in chemical composition of gases, liquids and chars. (19 refs.)

  19. Effect of oxidation on the chemical nature and distribution of low-temperature pyrolysis products from bituminous coal

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.; Ciavaglia, L.A.; MacPhee, J.A.; Nandi, B.N.; Vancea, L.

    1983-04-01

    Two bituminous coals, a high volatile Eastern Canadian and a medium volatile Western Canadian, were used to investigate the effect of oxidation on yields and chemical composition of gases, liquids and chars produced during coal pyrolysis. Pyrolysis experiments were performed at 500/sup 0/C using the Fischer assay method. Mild oxidation of coals resulted in a decrease of liquid hydrocarbon yields. Further coal oxidation increased the proportion of aromatic carbon in liquid products as determined by n.m.r., and also increased the content of oxygen in liquid products. The content of oxygen in chars was markedly lower than in corresponding coals. An attempt is made to explain reactions occurring during oxidation and subsequent pyrolysis of coal on the basis of differences in chemical composition of gases, liquids and chars.

  20. Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lv Tian [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Pan Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Liu Xinjuan; Lu Ting; Zhu Guang; Sun Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China)

    2011-10-13

    Highlights: > ZnO-reduced graphene oxide composite is synthesized via microwave assisted reaction. > The method allows a facile, safe and rapid reaction in aqueous media. > A high dye degradation efficiency is achieved under UV light irradiation. - Abstract: A quick and facile microwave-assisted reaction is used to synthesize ZnO-reduced graphene oxide (RGO) hybrid composites by reducing graphite oxide dispersion with zinc nitrate using a microwave synthesis system. Their photocatalytic performance in degradation of methylene blue is investigated and the results show that the RGO plays an important role in the enhancement of photocatalytic performance and the ZnO-RGO composite with 1.1 wt. % RGO achieves a maximum degradation efficiency of 88% in a neutral solution under UV light irradiation for 260 min as compared with pure ZnO (68%) due to the increased light absorption, the reduced charge recombination with the introduction of RGO.

  1. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  2. The Oil-Spill Snorkel: an innovative bioelectrochemical approach to accelerate hydrocarbons biodegradation in marine sediments

    Directory of Open Access Journals (Sweden)

    Carolina eCruz Viggi

    2015-09-01

    Full Text Available This study presents the proof-of-concept of the Oil-Spill Snorkel: a novel bioelectrochemical approach to stimulate the oxidative biodegradation of petroleum hydrocarbons in sediments. The Oil-Spill Snorkel consists of a single conductive material (the snorkel positioned suitably to create an electrochemical connection between the anoxic zone (the contaminated sediment and the oxic zone (the overlying O2-containing water. The segment of the electrode buried within the sediment plays a role of anode, accepting electrons deriving from the oxidation of contaminants. Electrons flow through the snorkel up to the part exposed to the aerobic environment (the cathode, where they reduce oxygen to form water. Here we report the results of lab-scale microcosms setup with marine sediments and spiked with crude oil. Microcosms containing 1 or 3 graphite snorkels and controls (snorkel-free and autoclaved were monitored for over 400 days. Collectively, the results of this study confirmed that the snorkels accelerate oxidative reactions taking place within the sediment, as documented by a significant 1.7-fold increase (p=0.023, two-tailed t-test in the cumulative oxygen uptake and 1.4-fold increase (p=0.040 in the cumulative CO2 evolution in the microcosms containing 3 snorkels compared to snorkel-free controls. Accordingly, the initial rate of total petroleum hydrocarbons (TPH degradation was also substantially enhanced. Indeed, while after 200 days of incubation a negligible degradation of TPH was noticed in snorkel-free controls, a significant reduction of 12±1% (p=0.004 and 21±1% (p=0.001 was observed in microcosms containing 1 and 3 snorkels, respectively. Although, the Oil-Spill Snorkel potentially represents a groundbreaking alternative to more expensive remediation options, further research efforts are needed to clarify factors and conditions affecting the snorkel-driven biodegradation processes and to identify suitable configurations for field

  3. Selective transformation of syngas into gasoline-range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles.

    Science.gov (United States)

    Cheng, Kang; Zhang, Lei; Kang, Jincan; Peng, Xiaobo; Zhang, Qinghong; Wang, Ye

    2015-01-26

    Bifunctional Fischer-Tropsch (FT) catalysts that couple uniform-sized Co nanoparticles for CO hydrogenation and mesoporous zeolites for hydrocracking/isomerization reactions were found to be promising for the direct production of gasoline-range (C5-11 ) hydrocarbons from syngas. The Brønsted acidity results in hydrocracking/isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the mesoporosity contributes to suppressing the formation of lighter (C1-4 ) hydrocarbons. The selectivity for C5-11 hydrocarbons could reach about 70 % with a ratio of isoparaffins to n-paraffins of approximately 2.3 over this catalyst, and the former is markedly higher than the maximum value (ca. 45 %) expected from the Anderson-Schulz-Flory distribution. By using n-hexadecane as a model compound, it was clarified that both the acidity and mesoporosity play key roles in controlling the hydrocracking reactions and thus contribute to the improved product selectivity in FT synthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames.

    Science.gov (United States)

    Ruwe, Lena; Moshammer, Kai; Hansen, Nils; Kohse-Höinghaus, Katharina

    2018-04-25

    In this study, we experimentally investigate the high-temperature oxidation kinetics of n-pentane, 1-pentene and 2-methyl-2-butene (2M2B) in a combustion environment using flame-sampling molecular beam mass spectrometry. The selected C5 fuels are prototypes for linear and branched, saturated and unsaturated fuel components, featuring different C-C and C-H bond structures. It is shown that the formation tendency of species, such as polycyclic aromatic hydrocarbons (PAHs), yielded through mass growth reactions increases drastically in the sequence n-pentane fuel-dependent reaction sequences of the gas-phase combustion mechanism that provide explanations for the observed difference in the PAH formation tendency. First, we investigate the fuel-structure-dependent formation of small hydrocarbon species that are yielded as intermediate species during the fuel decomposition, because these species are at the origin of the subsequent mass growth reaction pathways. Second, we review typical PAH formation reactions inspecting repetitive growth sequences in dependence of the molecular fuel structure. Third, we discuss how differences in the intermediate species pool influence the formation reactions of key aromatic ring species that are important for the PAH growth process underlying soot formation. As a main result it was found that for the fuels featuring a C[double bond, length as m-dash]C double bond, the chemistry of their allylic fuel radicals and their decomposition products strongly influences the combination reactions to the initially formed aromatic ring species and as a consequence, the PAH formation tendency.

  5. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Lina; Wang Wenjin; Hong Feng [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Yang Shengchun, E-mail: ysch1209@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); You Hongjun, E-mail: hjyou@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Fang Jixiang; Ding Bingjun [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China)

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  6. Iron oxide nanotube layer fabricated with electrostatic anodization for heterogeneous Fenton like reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Jun-Won; Park, Jae-Woo, E-mail: jaewoopark@hanyang.ac.kr

    2014-05-01

    Highlights: • Iron oxide nanotube was newly fabricated with potentiostatic anodization of Fe{sup 0} foil. • Cyanide was oxidized more effectively with the iron oxide nanotube and H{sub 2}O{sub 2}, resulting in fast oxidation of cyanide and cyanate. • This nanotube of Fe{sub 2}O{sub 3} on Fe{sup 0} metal can replace conventional particulate iron catalysts in Fenton-like processes. - Abstract: Iron oxide nanotubes (INT) were fabricated with potentiostatic anodization of zero valent iron foil in 1 M Na{sub 2}SO{sub 4} containing 0.5 wt% NH{sub 4}F electrolyte, holding the potential at 20, 40, and 60 V for 20 min, respectively. Field emission scanning electron microscopy and X-ray diffractometry were used to evaluate the morphology and crystalline structure of the INT film. The potential of 40 V for 20 min was observed to be optimal to produce an optimal catalytic film. Cyanide dissolved in water was degraded through the Fenton-like reaction using the INT film with hydrogen peroxide (H{sub 2}O{sub 2}). In case of INT-40 V in the presence of H{sub 2}O{sub 2} 3%, the first-order rate constant was found to be 1.7 × 10{sup −2} min{sup −1}, and 1.2 × 10{sup −2} min{sup −1} with commercial hematite powder. Degradation of cyanide was much less with only H{sub 2}O{sub 2}. Therefore, this process proposed in this work can be an excellent alternative to traditional catalysts for Fenton-like reaction.

  7. Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

    Science.gov (United States)

    Wang, Hui-Fang; Liu, Zhi-Pan

    2008-08-20

    Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

  8. The Synthesis, Characterization and Catalytic Reaction Studies of Monodisperse Platinum Nanoparticles in Mesoporous Oxide Materials

    Energy Technology Data Exchange (ETDEWEB)

    Rioux, Robert M. [Univ. of California, Berkeley, CA (United States)

    2006-01-01

    A catalyst design program was implemented in which Pt nanoparticles, either of monodisperse size and/or shape were synthesized, characterized and studied in a number of hydrocarbon conversion reactions. The novel preparation of these materials enables exquisite control over their physical and chemical properties that could be controlled (and therefore rationally tuned) during synthesis. The ability to synthesize rather than prepare catalysts followed by thorough characterization enable accurate structure-function relationships to be elucidated. This thesis emphasizes all three aspects of catalyst design: synthesis, characterization and reactivity studies. The precise control of metal nanoparticle size, surface structure and composition may enable the development of highly active and selective heterogeneous catalysts.

  9. Effect of strain on bond-specific reaction kinetics during the oxidation of H-terminated (111) Si

    International Nuclear Information System (INIS)

    Gokce, Bilal; Aspnes, David E.; Gundogdu, Kenan

    2011-01-01

    Although strain is used in semiconductor technology for manipulating optical, electronic, and chemical properties of semiconductors, the understanding of the microscopic phenomena that are affected or influenced by strain is still incomplete. Second-harmonic generation data obtained during the air oxidation of H-terminated (111) Si reveal the effect of compressive strain on this chemical reaction. Even small amounts of strain manipulate the reaction kinetics of surface bonds significantly, with tensile strain enhancing oxidation and compressive strain retarding it. This dramatic change suggests a strain-driven charge transfer mechanism between Si-H up bonds and Si-Si back bonds in the outer layer of Si atoms.

  10. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.; Dagaut, P.; Togbé , Casimir; Dayma, Guillaume; Sarathy, Mani; Westbrook, Charles K.; Egolfopoulos, Fokion N.

    2013-01-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  11. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.

    2013-09-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  12. Aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Roder, M.

    1985-01-01

    Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

  13. Polycyclic aromatic hydrocarbon metabolism in mullets, Chelon labrosus, treated by polychlorinated biphenyls

    International Nuclear Information System (INIS)

    Narbonne, J.F.; Suteau, P.; Daubeze, M.; Audy, C.

    1987-01-01

    Contamination of the ocean by hydrocarbons has become a major environmental problem. Consequently, it is not surprising that residues of potentially toxic xenobiotics, such as benzo(a)pyrene (B(a)P), are present in marine species used as human food. The oxidative metabolism of aromatic hydrocarbons proceeds via intermediate arene oxides. Some of these metabolites are very reactive electrophiles and may interact with cellular macromolecules such as proteins, DNA and RNA. Thus, the ability of an organism to further metabolize arene oxides can be an important protective mechanism against the possible toxic effect of these molecules. The existence of hepatic cytochrome P-450 dependent monooxygenase activities in fish is now well established. The exposure of fish to polychlorinated biphenyls (PCB) increases both the monooxygenase activities and the total amount of cytochrome P-450 in the microsomal fractions of fish liver. The purpose of this study was to compare the toxication-detoxication balance in both control and PCB induced estuarine fish (Grey mullets)

  14. Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

    2017-10-15

    Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

  15. Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

    Science.gov (United States)

    Jiang, Huanhuan; Jang, Myoseon; Sabo-Attwood, Tara; Robinson, Sarah E.

    2016-04-01

    The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

  16. Prediction of Petroleum Hydrocarbon Bioavailability in Contaminated Soils and Sediments

    NARCIS (Netherlands)

    Cuypers, M.P.; Clemens, R.; Grotenhuis, J.T.C.; Rulkens, W.H.

    2001-01-01

    Recently, several laboratory methods have been developed for the prediction of contaminant bioavailability. So far, none of these methods has been extensively tested for petroleum hydrocarbons. In the present study we investigated solid-phase extraction and persulfate oxidation for the prediction of

  17. Production of hydrogen from hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Lohmueller, R

    1984-03-01

    Hydrocarbons are the preferred starting materials for the industrial production of hydrogen. Most hydrogen is produced by steam reforming of light hydrocarbons. Partial oxidation of heavy oil and residue is used for the production of H/sub 2/ and synthesis gas in large plants. In both cases gas purification was improved. Hydrogen-rich gases like coke oven gas, refinery-offgas, and offgases from the chemical and petrochemical industry have high potential for becoming a major source of hydrogen. Processes for recovering H/sub 2/ (and by-products) are condensation and rectification at low temperatures and, most attractive and versatile for the production of very pure H/sub 2/, adsorption (PSA). The environmental impact of H/sub 2/ production lies mainly in the emission of CO/sub 2/ and heat. Other forms of pollution can be considerably reduced by conventional methods. The economy of H/sub 2/ production depends essentially on price and availability of the raw materials.

  18. Analysis of hydrocarbons generated in coalbeds

    Science.gov (United States)

    Butala, Steven John M.

    This dissertation describes kinetic calculations using literature data to predict formation rates and product yields of oil and gas at typical low-temperature conditions in coalbeds. These data indicate that gas formation rates from hydrocarbon thermolysis are too low to have generated commercial quantities of natural gas, assuming bulk first-order kinetics. Acid-mineral-catalyzed cracking, transition-metal-catalyzed hydrogenolysis of liquid hydrocarbons, and catalyzed CO2 hydrogenation form gas at high rates. The gaseous product compositions for these reactions are nearly the same as those for typical natural coalbed gases, while those from thermal and catalytic cracking are more representative of atypical coalbed gases. Three Argonne Premium Coals (Upper-Freeport, Pittsburgh #8 and Lewiston-Stockton) were extracted with benzene in both Soxhlet and elevated pressure extraction (EPE) systems. The extracts were compared on the basis of dry mass yield and hydrocarbon profiles obtained by gas chromatography/mass spectrometry. The dry mass yields for the Upper-Freeport coal gave consistent results by both methods, while the yields from the Pittsburgh #8 and Lewiston-Stockton coals were greater by the EPE method. EPE required ˜90 vol. % less solvent compared to Soxhlet extraction. Single-ion-chromatograms of the Soxhlet extracts all exhibited bimodal distributions, while those of the EPE extracts did not. Hydrocarbons analyzed from Greater Green River Basin samples indicate that the natural oils in the basin originated from the coal seams. Analysis of artificially produced oil indicates that hydrous pyrolysis mimics generation of C15+ n-alkanes, but significant variations were found in the branched alkane, low-molecular-weight n-alkanes, and high-molecular-weight aromatic hydrocarbon distributions.

  19. Process for the reduction of competitive oxidant consuming reactions in the solution mining of a mineral

    International Nuclear Information System (INIS)

    Stover, D.E.

    1980-01-01

    The present invention relates to an improved method for the solution mining of a mineral from a subterranean formation. More specifically, the invention relates to an improved method which enhances significantly the recovery of the mineral from a subterranean formation via solution mining by reducing the oxidant consuming reactions which compete with the mineral for the oxidant injected therein

  20. The Oxidative Metabolism of Fossil Hydrocarbons and Sulfide Minerals by the Lithobiontic Microbial Community Inhabiting Deep Subterrestrial Kupferschiefer Black Shale

    Directory of Open Access Journals (Sweden)

    Agnieszka Włodarczyk

    2018-05-01

    Full Text Available Black shales are one of the largest reservoirs of fossil organic carbon and inorganic reduced sulfur on Earth. It is assumed that microorganisms play an important role in the transformations of these sedimentary rocks and contribute to the return of organic carbon and inorganic sulfur to the global geochemical cycles. An outcrop of deep subterrestrial ~256-million-year-old Kupferschiefer black shale was studied to define the metabolic processes of the deep biosphere important in transformations of organic carbon and inorganic reduced sulfur compounds. This outcrop was created during mining activity 12 years ago and since then it has been exposed to the activity of oxygen and microorganisms. The microbial processes were described based on metagenome and metaproteome studies as well as on the geochemistry of the rock. The microorganisms inhabiting the subterrestrial black shale were dominated by bacterial genera such as Pseudomonas, Limnobacter, Yonghaparkia, Thiobacillus, Bradyrhizobium, and Sulfuricaulis. This study on black shale was the first to detect archaea and fungi, represented by Nitrososphaera and Aspergillus genera, respectively. The enzymatic oxidation of fossil aliphatic and aromatic hydrocarbons was mediated mostly by chemoorganotrophic bacteria, but also by archaea and fungi. The dissimilative enzymatic oxidation of primary reduced sulfur compounds was performed by chemolithotrophic bacteria. The geochemical consequences of microbial activity were the oxidation and dehydrogenation of kerogen, as well as oxidation of sulfide minerals.

  1. Oxidative removal of quinclorac by permanganate through a rate-limiting [3 + 2] cycloaddition reaction.

    Science.gov (United States)

    Song, Dean; Cheng, Hanyang; Jiang, Xiaohua; Sun, Huiqing; Kong, Fanyu; Liang, Rongning; Qiang, Zhimin; Liu, Huijuan; Qu, Jiuhui

    2018-04-05

    Quinclorac, a widely used herbicide in agriculture, has been recognized as an emerging environmental pollutant owing to its long persistence and potential risk to humans. However, no related information is available on the degradation of quinclorac by employing oxidants. Herein, the reactivity of quinclorac with permanganate was systematically investigated in water by combining experimental and computational approaches. The reaction followed overall second-order kinetics pointing to a bimolecular rate-limiting step. The second-order rate constant was found to be 3.47 × 10-3 M-1 s-1 at 25 °C, which was independent of pH over the range from 5 to 9 and was dependent on temperature over the range from 19 to 35 °C. The initial product was identified by UPLC-Q-TOF-MS to be mono-hydroxylated quinclorac, which was more susceptible to further oxidation. The result could be supported by the complete simulation of the reaction process in DFT calculations, indicating the [3 + 2] cycloaddition oxidation of the benzene ring in the rate-limiting step. The plausible mechanism was then proposed, accompanied by the analysis of the HOMO indicating the hydroxylation position and of the ESP suggesting a more electron-rich moiety. Considering the high effectiveness and low toxicity, permanganate oxidation was considered to be a very promising technique for removing quinclorac from aquatic environments.

  2. Surface oxidization-reduction reactions in Columbia Plateau basalts

    International Nuclear Information System (INIS)

    White, A.F.; Yee, A.

    1984-01-01

    Results are presented which define principal oxidation-reduction reactions expected between ground water and iron in the Umtanum and Cohassett basalt flows of south central Washington. Data include kinetics of aqueous iron speciation, rates of O 2 uptake and nature of oxyhydroxide precipitates. Such data are important in predicting behavior of radionuclides in basalt aquifers including determination of valence states, speciation, solubility, sorption, and coprecipitation on iron oxyhydroxide substrates and colloids. Analyses of the basalt by XPS indicates that ferrous iron is oxidized to ferric iron on the surface and that the total iron decreases as a function of pH during experimental weathering. Iron oxyhydroxide phases did not form surface coating on basalt surfaces but rather nucleated as separate plases in solution. No significant increases in Cs or Sr sorption were observed with increased weathering of the basalt. Concurrent increases in Fe(II) and decreases in Fe(III) in slightly to moderately acid solutions indicated continued oxidization of ferrous iron in the basalt. At neutral to basic pH, Fe(II) was strongly sorbed onto the basalt surface (Kd = 6.5 x 10 -3 1 x m 2 ) resulting in low dissolved concentrations even under anoxic conditions. The rate of O 2 uptake increased with decreasing pH. Diffusion rates (-- 10 -14 cm 2 x s -1 ), calculated using a one-dimensional analytical model, indicate grain boundary diffusion. Comparisons of Eh values calculated by Pt electrode, dissolved O 2 and Fe(II)/Fe(III) measurements showed considerable divergence, with the ferric-ferrous couple being the preferred method of estimating Eh

  3. Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom

    Science.gov (United States)

    2016-04-05

    acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H.sup. ions for Na.sup. ions. Carbon dioxide may be...extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide . The carbon dioxide and hydrogen may be used to produce hydrocarbons.

  4. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  5. Microwave-irradiation polyol synthesis of PVP-protected Pt–Ni electrocatalysts for methanol oxidation reaction

    CSIR Research Space (South Africa)

    Mathe, Ntombizodwa R

    2017-01-01

    Full Text Available ://doi.org/10.1007/s12678-017-0441-3 Microwave-Irradiation Polyol Synthesis of PVP-Protected Pt–Ni Electrocatalysts for Methanol Oxidation Reaction Ntombizodwa R. Mathe Manfred R. Scriba Rirhandzu S. Rikhotso Neil J. Coville ABSTRACT: Bimetallic Pt...

  6. Studies on the production of hydrocarbon mixtures from waste methyl ethyl ketone

    International Nuclear Information System (INIS)

    Kokitkar, P.B.; Roth, O.B.; Debelak, K.A.

    1992-01-01

    Large quantities of waste solvents are generated annually around the world in a large number of diverse industries, the paints and plastics industry being the largest consumer. The management of these waste solvents is becoming more and more difficult due to stricter environmental regulations by the EPA. The paint and allied products industry is expected to shift its solvent use from aliphatics and aromatics to oxygenated solvents to meet emissions and disposal standards. Many researchers have studied the dehydration reactions of oxygenated solvents to produce dehydration. However, most researchers have obtained only low molecular weight compounds (C 3 - C 4 hydrocarbons) from C 1 - C 4 alcohols and ketones. The kinetics of this class of reactions are not available in the open literature. The objective of this paper is to investigate the thermodynamic feasibility of this class of reactions and to compare the hydrocarbon products obtained using methylethyl ketone with regular unleaded gasoline

  7. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  8. Photodynamic activity of polycyclic hydrocarbon

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, S S

    1963-01-01

    Exposure of Paramecium caudatum to suspensions of 3,4-benzopyrene, followed by long wave ultraviolet irradiation, results in cell death at times related, inter alia, to carcinogen concentration. Prior to death, the cells exhibit progressive immobilization and blebbing. This photodynamic response is a sensitized photo-oxidation, as it is oxygen-dependent and inhibited by anti-oxidants, such as butylated hydroxy anisole and ..cap alpha..-tocopherol. Protection is also afforded by other agents, including Tweens, tryptophan and certain fractions of plasma proteins. No evidence was found for the involvement of peroxides or sulfhydryl groups. The correlations between photodynamic toxicity and carcinogenicity in a large series of polycyclic hydrocarbons is under investigation. Assays of air extracts for photodynamic toxicity are in progress. Significant toxicity has been found in oxygenated besides aromatic fractions.

  9. Near wall combustion modeling in spark ignition engines. Part B: Post-flame reactions

    International Nuclear Information System (INIS)

    Demesoukas, Sokratis; Caillol, Christian; Higelin, Pascal; Boiarciuc, Andrei; Floch, Alain

    2015-01-01

    Highlights: • Models for the post flame reactions (CO and hydrocarbons) and heat release rate are proposed. • ‘Freezing’ effect of CO kinetics is captured but equilibrium CO concentrations are low. • Reactive–diffusive processes are modeled for hydrocarbons and the last stage of combustion is captured. - Abstract: Reduced fuel consumption, low pollutant emissions and adequate output performance are key features in the contemporary design of spark ignition engines. Zero-dimensional numerical simulation is an attractive alternative to engine experiments for the evaluation of various engine configurations. Both flame front reaction and post-flame processes contribute to the heat release rate. The contribution of this work is to highlight and model the role of post-flame reactions (CO and hydrocarbons) in the heat release rate. The modeling approach to CO kinetics used two reactions considered to be dominant and thus more suitable for the description of CO chemical mechanism. Equilibrium concentrations of all the species involved were calculated by a two-zone thermodynamic model. The computed characteristic time of CO kinetics was found to be of a similar order to the results of complex chemistry simulations. The proposed model captured the ‘freezing’ effect (reaction rate is almost zero) for temperatures lower than 1800 K and followed the trends of the measured values at exhaust. However, a consistent underestimation of CO levels at the exhaust was observed. The impact of the remaining CO on the combustion efficiency is considerable especially for rich mixtures. For a remaining 0.4% CO mass fraction, the impact on combustion inefficiency is 0.1%. Unburnt hydrocarbon, which have not reacted within the flame front before quenching, diffuse in the burnt gas and react. In this work, a global reaction rate models the kinetic behavior of hydrocarbon. The diffusion process was modeled by a relaxation equation applied on the calculated kinetic concentration

  10. CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

    KAUST Repository

    Michalak, William D.; Krier, James M.; Alayoglu, Selim; Shin, Jae-Yoon; An, Kwangjin; Komvopoulos, Kyriakos; Liu, Zhi; Somorjai, Gabor A.

    2014-01-01

    The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn

  11. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  12. Reaction mechanisms and evaluation of effective process operation for catalytic oxidation and coagulation by ferrous solution and hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Moon, H.J.; Kim, Y.M. [Dept. of Environmental Engineering, Sangmyung Univ., Cheonan (Korea); Bae, W.K. [Dept. of Civil and Environmental Engineering, Hanyang Univ., Ansan, Kyounggi (Korea)

    2003-07-01

    This research was carried out to evaluate the removal efficiencies of COD{sub cr} and colour for the dyeing wastewater by ferrous solution and the different dosage of H{sub 2}O{sub 2} in Fenton process. In the case of H{sub 2}O{sub 2} divided dosage, 7:3 was more effective than 3:7 to remove COD{sub cr} and colour. The results showed that COD was mainly removed by Fenton coagulation, where the ferric ions are formed in the initial step of Fenton reaction. On the other hand colour was removed by Fenton oxidation rather than Fenton coagulation. This paper also aims at pursuing to investigate the effective removal mechanisms using ferrous ion coagulation, ferric ion coagulation and Fenton oxidation process. The removal mechanism of COD{sub cr} and colour was mainly coagulation by ferrous ion, ferric ion and Fenton oxidation. The removal efficiencies were dependent on the ferric ion amount at the beginning of the reaction. However the final removal efficiency of COD and colour was in the order of Fenton oxidation, ferric ion coagulation and ferrous ion coagulation. The reason of the highest removal efficiency by Fenton oxidation can be explained by the chain reactions with ferrous solution, ferric ion and hydrogen peroxide. (orig.)

  13. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitly...... molecules binding to bridging oxygens. The third chain interacts weakly and predominantly with the H2O molecules of the second layer, resembling bulk water. We find that the stability of the water layer close to the oxide surface is almost the same as the one found on flat metal surfaces, such as the Pt(111...... of RuO2 and IrO2, while it is increased by similar to 0.4 eV for TiO2....

  14. The reformation of liquid hydrocarbons in an aqueous discharge reactor

    International Nuclear Information System (INIS)

    Zhang, Xuming; Cha, Min Suk

    2015-01-01

    We present an aqueous discharge reactor for the reformation of liquid hydrocarbons. To increase a dielectric constant of a liquid medium, we added distilled water to iso-octane and n-dodecane. As expected, we found decreased discharge onset voltage and increased discharge power with increased water content. Results using optical emission spectroscopy identified OH radicals and O atoms as the predominant oxidative reactive species with the addition of water. Enriched CH radicals were also visualized, evidencing the existence of cascade carbon–carbon cleavage and dehydrogenation processes in the aqueous discharge. The gaseous product consisted primarily of hydrogen, carbon monoxide, and unsaturated hydrocarbons. The composition of the product was readily adjustable by varying the volume of water added, which demonstrated a significant difference in composition with respect to the tested liquid hydrocarbon. In this study, we found no presence of CO 2 emissions or the contamination of the reactor by solid carbon deposition. These findings offer a new approach to the reforming processes of liquid hydrocarbons and provide a novel concept for the design of a practical and compact plasma reformer. (paper)

  15. Hydrogen production with short contact time. Catalytic partial oxidation of hydrocarbons and oxygenated compounds: Recent advances in pilot- and bench-scale testing and process design

    Energy Technology Data Exchange (ETDEWEB)

    Guarinoni, A.; Ponzo, R.; Basini, L. [ENI Refining and Marketing Div., San Donato Milanese (Italy)

    2010-12-30

    ENI R and D has been active for fifteen years in the development of Short Contact Time - Catalytic Partial Oxidation (SCT-CPO) technologies for producing Hydrogen/Synthesis Gas. From the beginning the experimental work addressed either at defining the fundamental principles or the technical and economical potential of the technology. Good experimental responses, technical solutions' simplicity and flexibility, favourable techno-economical evaluations promoted the progressive widening of the field of the investigations. From Natural Gas (NG) the range of ''processable'' Hydrocarbons extended to Liquefied Petroleum Gas (LPG) and Gasoils, including those characterised by high levels of unsaturated and sulphurated molecules and, lately, to other compounds with biological origin. The extensive work led to the definition of different technological solutions, grouped as follows: Technology 1: Air Blown SCT-CPO of Gaseous Hydrocarbons and/or Light Compounds with biological origin Technology 2: Enriched Air/Oxygen Blown SCT-CPO of Gaseous Hydrocarbons and/or Light Compounds with biological origin Technology 3: Enriched Air/Oxygen Blown SCT-CPO of Liquid Hydrocarbons and/or Compounds with biological origin Recently, the licence rights on a non-exclusive basis for the commercialisation of SCT-CPO based processes for H{sub 2}/Synthesis gas production from light hydrocarbons with production capacity lower than 5,000 Nm{sup 3}/h of H{sub 2} or 7,500 Nm3/h of syngas have been assigned to two external companies. In parallel, development of medium- and large-scale plant solutions is progressing within the ENI group framework. These last activities are addressed to the utilisation of SCT-CPO for matching the variable Hydrogen demand in several contexts of oil refining operation. This paper will report on the current status of SCT-CPO with a focus on experimental results obtained, either at pilot- and bench- scale level. (orig.)

  16. External heavy atom effect on intersystem crossing reactions of aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Wojnarovits, L.; Foeldiak, G.

    1988-01-01

    The external heavy atom effect by xenon on the S 1 → T n and T 1 → S o transitions of naphthalene and pyrene was investigated in hydrocarbon solvents by fluorescence or absorption spectroscopy. The quencher forms a short-lived encounter complex (that may be called exciplex as well) with the excited molecules in equilibrium process. This exciplex formation in solutions with naphthalene leads to some deviation from the Stern-Volmer type concentration dependence of the quenching. (author)

  17. A DFT study on the enthalpies of thermite reactions and enthalpies of formation of metal composite oxide

    Science.gov (United States)

    Zhang, Yu-ying; Wang, Meng-jie; Chang, Chun-ran; Xu, Kang-zhen; Ma, Hai-xia; Zhao, Feng-qi

    2018-05-01

    The standard thermite reaction enthalpies (ΔrHmθ) for seven metal oxides were theoretically analyzed using density functional theory (DFT) under five different functional levels, and the results were compared with experimental values. Through the comparison of the linear fitting constants, mean error and root mean square error, the Perdew-Wang functional within the framework of local density approximation (LDA-PWC) and Perdew-Burke-Ernzerhof exchange-correlation functional within the framework of generalized gradient approximation (GGA-PBE) were selected to further calculate the thermite reaction enthalpies for metal composite oxides (MCOs). According to the Kirchhoff formula, the standard molar reaction enthalpies for these MCOs were obtained and their standard molar enthalpies of formation (ΔfHmθ) were finally calculated. The results indicated that GGA-PBE is the most suitable one out of the total five methods to calculate these oxides. Tungstate crystals present the maximum deviation of the enthalpies of thermite reactions for MCOs and these of their physical metal oxide mixtures, but ferrite crystals are the minimum. The correlation coefficients are all above 0.95, meaning linear fitting results are very precise. And the molar enthalpies of formation for NiMoO4, CuMoO4, PbZrO3 (Pm/3m), PbZrO3 (PBA2), PbZrO3 (PBam), MgZrO3, CdZrO3, MnZrO3, CuWO4 and Fe2WO6 were first obtained as -1078.75, -1058.45, -1343.87, -1266.54, -1342.29, -1333.03, -1210.43, -1388.05, -1131.07 and - 1860.11 kJ·mol-1, respectively.

  18. High resolution X-ray photoelectron spectroscopy of styrene oxide adsorption and reaction on Ag(1 1 1)

    Science.gov (United States)

    Piao, H.; Enever, M. C. N.; Adib, K.; Hrbek, J.; Barteau, M. A.

    2004-11-01

    Synchrotron-based X-ray photoelectron spectroscopy (XPS) has been used to investigate the adsorption and reaction of styrene oxide on Ag(1 1 1). When adsorption is carried out at 250 K or above, ring opening of styrene oxide forms a stable surface oxametallacycle intermediate which eventually reacts at 485 K to regenerate styrene oxide. High resolution XPS is capable of distinguishing the oxametallacycle from molecularly adsorbed and condensed styrene oxide on the basis of different C1s peak separations. The observed separations are well accounted for by the results of DFT calculations.

  19. Reactivity of hydrocarbons in response to injection of a CO2/O2 mixture under depleted reservoir conditions: experimental and numerical modeling

    International Nuclear Information System (INIS)

    Pacini-Petitjean, Claire

    2015-01-01

    The geological storage of CO 2 (CO 2 Capture-Storage - CCS) and the Enhanced Oil Recovery (EOR) by CO 2 injection into petroleum reservoirs could limit CO 2 atmospheric accumulation. However, CO 2 can be associated with oxygen. To predict the hydrocarbon evolution under these conditions involves the study of oxidation mechanisms. Oxidation experiment and kinetic detailed modeling were carried out with pure compounds. The comparison between experimental and modeling results led to the construction of a hydrocarbon oxidation kinetic model and emphasized the parameters leading to auto ignition. The good agreement between our experiments and modeling are promising for the development of a tool predicting the critical temperature leading to auto-ignition and the evolution of hydrocarbon composition, to estimate the stability of a petroleum system in CO 2 injection context. (author) [fr

  20. Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

    KAUST Repository

    Liu, Zhaohui; Dong, Xinglong; Liu, Xin; Han, Yu

    2016-01-01

    Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences