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Sample records for catalyzed hydrocarbon formation

  1. Practical carbon-carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation.

    Science.gov (United States)

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  2. Transfer Methane to Fragrant Hydrocarbon by Direct Catalyzed Dehydrogenation

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ Sponsored by NSFC,a research project -"Transfer methane to fragrant hydrocarbon by direct catalyzed dehydrogenation",directed by Prof.Xin Bao from Dalian Institute of Chemical Physics of CAS,honored the 2nd class National Science & Technology Award in 2005.

  3. GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II

    Science.gov (United States)

    Green Catalyzed Oxidation of Hydrocarbons in Alternative Solvent Systems Generated by PARIS IIMichael A. Gonzalez*, Thomas M. Becker, and Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26...

  4. Hydrogenation of unsaturated hydrocarbons catalyzed by palladium complexes. [Phenylacetylene

    Energy Technology Data Exchange (ETDEWEB)

    Levkovskii, Y.S.; Ryutina, N.M.; Shmidt, F.K.

    1980-06-01

    Hydrogenation of unsaturated hydrocarbons catalyzed by palladium complexes obtained by reducing Pd(II) stearate or acetylacetonate (AcAc) with triethylaluminum was studied at 30/sup 0/C in toluene solutions. Hydrogenation of phenylacetylene in the presence of Pd(AcAc)/sub 2/ and Al(C/sub 2/H/sub 5/)/sub 3/ at 0.005 mole/l. Pd and 2:1 Al/Pd occurred much more rapidly than in the absence of Al(C/sub 2/H/sub 5/)/sub 3/ and gave ethylbenzene as the only product. Subsequent addition of organic phosphines, e.g., P(C/sub 6/H/sub 5/)/sub 3/ or P(C/sub 4/H/sub 9/)/sub 3/, shifted the reaction toward styrene, which was obtained with up to 98% selectivity at 4:1 P/Pd. P(C/sub 4/H/sub 9/)/sub 3/ also strongly increased the reaction rate. Addition of phosphines before Al(C/sub 2/H/sub 5/)/sub 3/ produced systems with low activities. Hydrogenation of isoprene in the presence of Pd(II) compounds and Al (C/sub 2/H/sub 5/) occurred at as low as 10/sup 0/C and gave isopentane and methylbutene isomers. The selectivity for the latter at 95% isoprene conversion was increased from 84 to 99.8% by the addition of phosphines to 6:1 P/Pd. Phosphines also had an activating effect which increased in the order P(C/sub 6/H/sub 5/)/sub 3/ < P(C/sub 4/H/sub 9/)/sub 3/ < P(C/sub 6/H/sub 11/)/sub 3/.

  5. Cogeneration systems and processes for treating hydrocarbon containing formations

    Science.gov (United States)

    Vinegar, Harold J.; Fowler, Thomas David; Karanikas, John Michael

    2009-12-29

    A system for treating a hydrocarbon containing formation includes a steam and electricity cogeneration facility. At least one injection well is located in a first portion of the formation. The injection well provides steam from the steam and electricity cogeneration facility to the first portion of the formation. At least one production well is located in the first portion of the formation. The production well in the first portion produces first hydrocarbons. At least one electrical heater is located in a second portion of the formation. At least one of the electrical heaters is powered by electricity from the steam and electricity cogeneration facility. At least one production well is located in the second portion of the formation. The production well in the second portion produces second hydrocarbons. The steam and electricity cogeneration facility uses the first hydrocarbons and/or the second hydrocarbons to generate electricity.

  6. Formation Mechanism of the First Carbon-Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons.

    Science.gov (United States)

    Liu, Yue; Müller, Sebastian; Berger, Daniel; Jelic, Jelena; Reuter, Karsten; Tonigold, Markus; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-05-01

    The elementary reactions leading to the formation of the first carbon-carbon bond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst. This carbonylation based mechanism has an energy barrier of 80 kJ mol(-1) for the formation of the first C-C bond, in line with a broad range of experiments, and significantly lower than the barriers associated with earlier proposed mechanisms. PMID:27037603

  7. Insights into Hydrocarbon Formation by Nitrogenase Cofactor Homologs

    OpenAIRE

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

    2015-01-01

    IMPORTANCE 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 us...

  8. Heating hydrocarbon containing formations in a line drive staged process

    Science.gov (United States)

    Miller, David Scott

    2009-07-21

    Method for treating a hydrocarbon containing formation are described herein. Methods may include providing heat to a first section of the formation with one or more first heaters in the first section. First hydrocarbons may be heated in the first section such that at least some of the first hydrocarbons are mobilized. At least some of the mobilized first hydrocarbons may be produced through a production well located in a second section of the formation. The second section may be located substantially adjacent to the first section. A portion of the second section may be provided some heat from the mobilized first hydrocarbons, but is not conductively heated by heat from the first heaters. Heat may be provided to the second section with one or more second heaters in the second section to further heat the second section.

  9. Laboratory Investigation of Organic Aerosol Formation from Aromatic Hydrocarbons

    Science.gov (United States)

    Molina, Luisa T.; Molina, Mario J.; Zhang, Renyi

    2006-08-23

    Our work for this DOE funded project includes: (1) measurements of the kinetics and mechanism of the gas-phase oxidation reactions of the aromatic hydrocarbons initiated by OH; (2) measurements of aerosol formation from the aromatic hydrocarbons; and (3) theoretical studies to elucidate the OH-toluene reaction mechanism using quantum-chemical and rate theories.

  10. Porous silicon formation during Au-catalyzed etching

    International Nuclear Information System (INIS)

    The formation of “black” nano-textured Si during the Au-catalyzed wet-chemical etch process was investigated with respect to photovoltaic applications. Cross-sectional scanning electron microscopy (SEM) images recorded at different stages of the etch process exhibit an evolution of a two-layer structure, consisting of cone-like Si hillocks covered with a nano-porous Si (np-Si) layer. Optical measurements confirm the presence of a np-Si phase which appears after the first ∼10 s of the etch process and continuously increases with the etch time. Furthermore, the etch process was investigated on Si substrates with different doping levels (∼0.01–100 Ω cm). SEM images show a transition from the two-layer morphology to a structure consisting entirely of np-Si for higher doping levels (<0.1 Ω cm). The experimental results are discussed on the basis of the model of a local electrochemical etch process. A better understanding of the metal-catalyzed etch process facilitates the fabrication of “black” Si on various Si substrates, which is of significant interest for photovoltaic applications

  11. Formation and preservation of liquid hydrocarbon accumulations at great depths

    Energy Technology Data Exchange (ETDEWEB)

    Akramkhodzhaev, A.M.; Kirshin, A.V.; Kushnir, M.I.

    1980-01-01

    Based on an analysis and comparison of the change in the concentration of hydrocarbons in insoluble organic matter as depth is increased and of the change in the intensity of sapropel-based production of bitumens, it is demonstrated that the repeat accumulation of liquid hydrocarbon in the insoluble organic matter precedes the lower generation maximum. Structural changes in the kerogen at the end of the primary oil generation and emigration phase are favorable factors for the accumulation of these hydrocarbons. A hyphothesis on the mechanism for oil pool formation and preservation at great depths is expressed.

  12. GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II DECHEMA; GREEN SOLVENTS FOR CATALYSIS - ENVIRONMENTALLY BENIGN REACTION MEDIA

    Science.gov (United States)

    Green catalyzed oxidation of hydrocarbons in alternative solvent systems generated by PARIS IIThomas M. Becker, Michael A. Gonzalez, Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Mar...

  13. Irregular spacing of heat sources for treating hydrocarbon containing formations

    Science.gov (United States)

    Miller, David Scott; Uwechue, Uzo Philip

    2012-06-12

    A method for treating a hydrocarbon containing formation includes providing heat input to a first section of the formation from one or more heat sources located in the first section. Fluids are produced from the first section through a production well located at or near the center of the first section. The heat sources are configured such that the average heat input per volume of formation in the first section increases with distance from the production well.

  14. Short Synthesis of Sulfur Analogues of Polyaromatic Hydrocarbons through Three Palladium-Catalyzed C-H Bond Arylations.

    Science.gov (United States)

    Hagui, Wided; Besbes, Néji; Srasra, Ezzeddine; Roisnel, Thierry; Soulé, Jean-François; Doucet, Henri

    2016-09-01

    An expeditious synthesis of a wide range of phenanthro[9,10-b]thiophene derivatives, which are a class of polyaromatic hydrocarbon (PAH) containing a sulfur atom, is reported. The synthetic scheme involves only two operations from commercially available thiophenes, 2-bromobenzenesulfonyl chlorides and aryl bromides. In the first step, palladium-catalyzed desulfitative arylation using 2-bromobenzenesulfonyl chlorides allows the synthesis of thiophene derivatives, which are substituted at the C4 position by an aryl group containing an ortho-bromo substituent. Then, a palladium-catalyzed one-pot cascade intermolecular C5-arylation of thiophene using aryl bromides followed by intramolecular arylation led to the corresponding phenanthro[9,10-b]thiophenes in a single operation. In addition, PAHs containing two or three sulfur atoms, as well as both sulfur and nitrogen atoms, were also designed by this strategy. PMID:27550151

  15. Solution mining systems and methods for treating hydrocarbon containing formations

    Science.gov (United States)

    Vinegar, Harold J.; de Rouffignac, Eric Pierre; Schoeling, Lanny Gene

    2009-07-14

    A method for treating an oil shale formation comprising nahcolite is disclosed. The method includes providing a first fluid to a portion of the formation through at least two injection wells. A second fluid is produced from the portion through at least one injection well until at least two injection wells are interconnected such that fluid can flow between the two injection wells. The second fluid includes at least some nahcolite dissolved in the first fluid. The first fluid is injected through one of the interconnected injection wells. The second fluid is produced from at least one of the interconnected injection wells. Heat is provided from one or more heaters to the formation to heat the formation. Hydrocarbon fluids are produced from the formation.

  16. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels

    DEFF Research Database (Denmark)

    Peterson, Andrew; Abild-Pedersen, Frank; Studt, Felix;

    2010-01-01

    Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels.......Density functional theory calculations explain copper's unique ability to convert CO2 into hydrocarbons, which may open up (photo-)electrochemical routes to fuels....

  17. Formation of charged nanoparticles in hydrocarbon flames: principal mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Starik, A M; Savel' ev, A M; Titova, N S [Central Institute of Aviation Motors, 2 Aviamotornaya st., 111116 Moscow (Russian Federation)], E-mail: star@ciam.ru

    2008-11-01

    The processes of charged gaseous and particulate species formation in sooting hydrocarbon/air flame are studied. The original kinetic model, comprising the chemistry of neutral and charged gaseous species, generation of primary clusters, which then undergo charging due to attachment of ions and electrons to clusters and via thermoemission, and coagulation of charged-charged, charged-neutral and neutral-neutral particles, is reported. The analysis shows that the principal mechanisms of charged particle origin in hydrocarbon flames are associated with the attachment of ions and electrons produced in the course of chemoionization reactions to primary small clusters and particles and coagulation via charged-charged and charged-neutral particle interaction. Thermal ionization of particles does not play a significant role in the particle charging.

  18. Formation of charged nanoparticles in hydrocarbon flames: principal mechanisms

    Science.gov (United States)

    Starik, A. M.; Savel'ev, A. M.; Titova, N. S.

    2008-11-01

    The processes of charged gaseous and particulate species formation in sooting hydrocarbon/air flame are studied. The original kinetic model, comprising the chemistry of neutral and charged gaseous species, generation of primary clusters, which then undergo charging due to attachment of ions and electrons to clusters and via thermoemission, and coagulation of charged-charged, charged-neutral and neutral-neutral particles, is reported. The analysis shows that the principal mechanisms of charged particle origin in hydrocarbon flames are associated with the attachment of ions and electrons produced in the course of chemoionization reactions to primary small clusters and particles and coagulation via charged-charged and charged-neutral particle interaction. Thermal ionization of particles does not play a significant role in the particle charging. This paper was presented at the Third International Symposium on Nonequilibrium Process, combustion, and Atmospheric Phenomena (Dagomys, Sochi, Russia, 25-29 June 2007).

  19. Formation of charged nanoparticles in hydrocarbon flames: principal mechanisms

    International Nuclear Information System (INIS)

    The processes of charged gaseous and particulate species formation in sooting hydrocarbon/air flame are studied. The original kinetic model, comprising the chemistry of neutral and charged gaseous species, generation of primary clusters, which then undergo charging due to attachment of ions and electrons to clusters and via thermoemission, and coagulation of charged-charged, charged-neutral and neutral-neutral particles, is reported. The analysis shows that the principal mechanisms of charged particle origin in hydrocarbon flames are associated with the attachment of ions and electrons produced in the course of chemoionization reactions to primary small clusters and particles and coagulation via charged-charged and charged-neutral particle interaction. Thermal ionization of particles does not play a significant role in the particle charging.

  20. Heating hydrocarbon containing formations in a spiral startup staged sequence

    Science.gov (United States)

    Vinegar, Harold J.; Miller, David Scott

    2009-12-15

    Methods for treating a hydrocarbon containing formation are described herein. Methods may include treating a first zone of the formation. Treatment of a plurality of zones of the formation may be begun at selected times after the treatment of the first zone begins. The treatment of at least two successively treated zones may begin at a selected time after treatment of the previous zone begins. At least two of the successively treated zones may be adjacent to the zone treated previously. The successive treatment of the zones proceeds in an outward, substantially spiral sequence from the first zone so that the treatment of the zones may move substantially spirally outwards towards a boundary of the treatment area.

  1. Predicting hydrocarbon potential of an earth formation underlying water

    International Nuclear Information System (INIS)

    A method for the on-site collection and examination of small concentrations of a carbonaceous gas, e.g. methane, dissolved in a body of water overlying an earth formation to predict hydrocarbon potential of the earth formation under the body of water, the formation being a source of carbonaceous gas, comprises at a known geographic location sampling the water at a selected flow rate and at a selected depth; continuously vacuum separating the water into liquid and gas phases; separating a selected carbonaceous gas from interfering gas species in the presence of an air carrier vented to atmosphere at a known flow rate; and quantitatively oxidizing the selected gas and then cryogenically trapping an oxidant thereof in the presence of said air carrier to provide for an accurate isotopic examination. (author)

  2. Experimental investigation of magnetic mineral formation in hydrocarbon environments

    Science.gov (United States)

    Abubakar, Rabiu; Muxworthy, Adrian; Sephton, Mark; Fraser, Alastair

    2013-04-01

    Experimental investigation of magnetic mineral formation in hydrocarbon environments Rabiu Abubakar, Adrian Muxworthy, Mark Septhon and Alastair Fraser Dept. of Earth Science and Engineering, Imperial College London Magnetic anomalies have been observed over oil fields from aeromagnetic surveys. These anomalies have been linked with the presence of hydrocarbons and that has generated a lot of interest over possible application of magnetism in the exploration of oil and gas but there has also been debate over the origin of the magnetic minerals causing the magnetic anomaly. Our approach was to generate crude oil in the lab using three source rocks from the Wessex Basin, England, which is a hydrocarbon province. The source rocks were the Kimmeridge Clay, Oxford Clay and the Blue Lias. The source rocks were powered and pyrolysed in a high pressure vessel. The crude oil was then extracted and the magnetic signal of the remaining pyrolysate measured. We discovered a significant contrast in the magnetic hysteresis and thermomagnetic properties between the pyrolysate and the unpyrolysed (immature) source rocks. We will present the preliminary results, which indicate that magnetic minerals were generated as a result of heat and therefore related linked to maturation of the source rocks

  3. Polycyclic aromatic hydrocarbons' formation and occurrence in processed food.

    Science.gov (United States)

    Singh, Lochan; Varshney, Jay G; Agarwal, Tripti

    2016-05-15

    Polycyclic aromatic hydrocarbons (PAHs) emerged as an important contaminant group in a gamut of processed food groups like dairy, nuts, herbs, beverages, meat products etc. Different cooking processes and processing techniques like roasting, barbecuing, grilling, smoking, heating, drying, baking, ohmic-infrared cooking etc. contribute towards its formation. The level of PAHs depends on factors like distance from heat source, fuel used, level of processing, cooking durations and methods, whereas processes like reuse, conching, concentration, crushing and storage enhance the amount of PAHs in some food items. This review paper provides insight into the impact of dietary intake of PAHs, its levels and formation mechanism in processed food items and possible interventions for prevention and reduction of the PAHs contamination. The gaps and future prospects have also been assessed. PMID:26776034

  4. Moving hydrocarbons through portions of tar sands formations with a fluid

    Science.gov (United States)

    Stegemeier, George Leo; Mudunuri, Ramesh Raju; Vinegar, Harold J.; Karanikas, John Michael; Jaiswal, Namit; Mo, Weijian

    2010-05-18

    A method for treating a tar sands formation is disclosed. The method includes heating a first portion of a hydrocarbon layer in the formation from one or more heaters located in the first portion. The heat is controlled to increase a fluid injectivity of the first portion. A drive fluid and/or an oxidizing fluid is injected and/or created in the first portion to cause at least some hydrocarbons to move from a second portion of the hydrocarbon layer to a third portion of the hydrocarbon layer. The second portion is between the first portion and the third portion. The first, second, and third portions are horizontally displaced from each other. The third portion is heated from one or more heaters located in the third portion. Hydrocarbons are produced from the third portion of the formation. The hydrocarbons include at least some hydrocarbons from the second portion of the formation.

  5. Biofuel-Promoted Polychlorinated Dibenzodioxin/furan Formation in an Iron-Catalyzed Diesel Particle Filter.

    Science.gov (United States)

    Heeb, Norbert V; Rey, Maria Dolores; Zennegg, Markus; Haag, Regula; Wichser, Adrian; Schmid, Peter; Seiler, Cornelia; Honegger, Peter; Zeyer, Kerstin; Mohn, Joachim; Bürki, Samuel; Zimmerli, Yan; Czerwinski, Jan; Mayer, Andreas

    2015-08-01

    Iron-catalyzed diesel particle filters (DPFs) are widely used for particle abatement. Active catalyst particles, so-called fuel-borne catalysts (FBCs), are formed in situ, in the engine, when combusting precursors, which were premixed with the fuel. The obtained iron oxide particles catalyze soot oxidation in filters. Iron-catalyzed DPFs are considered as safe with respect to their potential to form polychlorinated dibenzodioxins/furans (PCDD/Fs). We reported that a bimetallic potassium/iron FBC supported an intense PCDD/F formation in a DPF. Here, we discuss the impact of fatty acid methyl ester (FAME) biofuel on PCDD/F emissions. The iron-catalyzed DPF indeed supported a PCDD/F formation with biofuel but remained inactive with petroleum-derived diesel fuel. PCDD/F emissions (I-TEQ) increased 23-fold when comparing biofuel and diesel data. Emissions of 2,3,7,8-TCDD, the most toxic congener [toxicity equivalence factor (TEF) = 1.0], increased 90-fold, and those of 2,3,7,8-TCDF (TEF = 0.1) increased 170-fold. Congener patterns also changed, indicating a preferential formation of tetra- and penta-chlorodibenzofurans. Thus, an inactive iron-catalyzed DPF becomes active, supporting a PCDD/F formation, when operated with biofuel containing impurities of potassium. Alkali metals are inherent constituents of biofuels. According to the current European Union (EU) legislation, levels of 5 μg/g are accepted. We conclude that risks for a secondary PCDD/F formation in iron-catalyzed DPFs increase when combusting potassium-containing biofuels. PMID:26176879

  6. Degradation of polycyclic aromatic hydrocarbons by hydrogen peroxide catalyzed by heterogeneous polymeric metal chelates

    Czech Academy of Sciences Publication Activity Database

    Baldrian, Petr; Cajthaml, Tomáš; Merhautová, Věra; Gabriel, Jiří; Nerud, František; Stopka, P.; Hrubý, Martin; Beneš, Milan J.

    2005-01-01

    Roč. 59, - (2005), s. 267-274. ISSN 0926-3373 R&D Projects: GA AV ČR IBS5020306; GA ČR GA203/01/0944 Institutional research plan: CEZ:AV0Z7090911 Keywords : degradation * polycyclic aromatic hydrocarbon * hydrogen peroxide Subject RIV: EE - Microbiology, Virology Impact factor: 3.809, year: 2005

  7. Interconversion between formate and hydrogen carbonate by tungsten-containing formate dehydrogenase-catalyzed mediated bioelectrocatalysis

    Directory of Open Access Journals (Sweden)

    Kento Sakai

    2015-09-01

    Full Text Available We have focused on the catalytic properties of tungsten-containing formate dehydrogenase (FoDH1 from Methylobacterium extorquens AM1 to construct a bioelectrochemical interconversion system between formate (HCOO− and hydrogen carbonate (HCO3−. FoDH1 catalyzes both of the HCOO oxidation and the HCO3− reduction with several artificial dyes. The bi-molecular reaction rate constants between FoDH1 and the artificial electron acceptors and NAD+ (as the natural electron acceptor show the property called a linear free energy relationship (LFER, indicating that FoDH1 would have no specificity to NAD+. Similar LFER is also observed for the catalytic reduction of HCO3−. The reversible reaction between HCOO− and HCO3− through FoDH1 has been realized on cyclic voltammetry by using methyl viologen (MV as a mediator and by adjusting pH from the thermodynamic viewpoint. Potentiometric measurements have revealed that the three redox couples, MV2+/MV·−+, HCOO−/HCO3−, FoDH1 (ox/red, reach an equilibrium in the bulk solution when the two-way bioelectrocatalysis proceeds in the presence of FoDH1 and MV. The steady-state voltammograms with two-way bioelectrocatalytic properties are interpreted on a simple model by considering the solution equilibrium.

  8. Polycyclic aromatic hydrocarbon formation under simulated coal seam pyrolysis conditions

    Institute of Scientific and Technical Information of China (English)

    Liu Shuqin; Wang Yuanyuan; Wang Caihong; Bao Pengcheng; Dang Jinli

    2011-01-01

    Coal seam pyrolysis occurs during coal seam fires and during underground coal gasification.This is an important source of polycyclic aromatic hydrocarbon (PAH) emission in China.Pyrolysis in a coal seam was simulated in a tubular furnace.The 16 US Environmental Protection Agency priority controlled PAHs were analyzed by HPLC.The effects of temperature,heating rate,pyrolysis atmosphere,and coal size were investigated.The results indicate that the 3-ring PAHs AcP and AcPy are the main species in the pyrolysis gas.The 2-ring NaP and the 4-ring Pyr are also of concern.Increasing temperature caused the total PAH yield to go through a minimum.The lowest value was obtained at the temperature of 600 ℃ Higher heating rates promote PAH formation,especially formation of the lower molecular weight PAHs.The typical heating rate in a coal seam,5 ℃/min,results in intermediate yields of PAHs.The total PAHs yield in an atmosphere of N2 is about 1.81 times that seen without added N2,which indicates that an air flow through the coal seam accelerates the formation of PAHs.An increase in coal particle size reduces the total PAHs emission but promotes the formation of 5- and 6-ring PAHs.

  9. Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2.

    Science.gov (United States)

    Juliá-Hernández, Francisco; Gaydou, Morgane; Serrano, Eloisa; van Gemmeren, Manuel; Martin, Ruben

    2016-08-01

    The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species. PMID:27573397

  10. Apparatus for hydrogen and carbon production via carbon aerosol-catalyzed dissociation of hydrocarbons

    Science.gov (United States)

    Muradov, Nazim Z. (Inventor); Smith, Franklyn (Inventor); Tabatabaie-Raissi, Ali (Inventor)

    2012-01-01

    A novel process and apparatus is disclosed for sustainable, continuous production of hydrogen and carbon by catalytic dissociation or decomposition of hydrocarbons at elevated temperatures using in-situ generated carbon particles. Carbon particles are produced by decomposition of carbonaceous materials in response to an energy input. The energy input can be provided by at least one of a non-oxidative and oxidative means. The non-oxidative means of the energy input includes a high temperature source, or different types of plasma, such as, thermal, non-thermal, microwave, corona discharge, glow discharge, dielectric barrier discharge, or radiation sources, such as, electron beam, gamma, ultraviolet (UV). The oxidative means of the energy input includes oxygen, air, ozone, nitrous oxide (NO.sub.2) and other oxidizing agents. The method, apparatus and process of the present invention is applicable to any gaseous or liquid hydrocarbon fuel and it produces no or significantly less CO.sub.2 emissions compared to conventional processes.

  11. Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Poreddy, Raju; Engelbrekt, Christian; Kegnæs, Søren

    2014-01-01

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions...

  12. The formation of polycyclic aromatic hydrocarbons in evolved circumstellar environments

    CERN Document Server

    Cherchneff, Isabelle

    2010-01-01

    The formation of Polycyclic Aromatic Hydrocarbons in the circumstellar outflows of evolved stars is reviewed, with an emphasis on carbon stars on the Asymptotic Giant Branch. Evidence for PAHs present in their winds is provided by meteoritic studies and recent observations of the Unidentified Infrared bands. We detail the chemical processes leading to the closure of the first aromatic ring as well as the growth mechanisms leading to amorphous carbon grains. Existing studies on PAH formation in evolved stellar envelopes are reviewed and new results for the modelling of the inner wind of the archetype carbon star IRC+10216 are presented. Benzene, C6H6, forms close to the star, as well as water, H2O, as a result of non-equilibrium chemistry induced by the periodic passage of shocks. The growth process of aromatic rings may thus resemble that active in sooting flames due to the presence of radicals like hydroxyl, OH. Finally, we discuss possible formation processes for PAHs and aromatic compounds in the hydrogen-...

  13. Methane Decomposition and C2 Hydrocarbon Formation under the Condition of DC Discharge Plasma

    Institute of Scientific and Technical Information of China (English)

    Jianxun He; Miao Hu; Zhiguo Lu

    2004-01-01

    The infrared emission spectra of methane, H, CH and C2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C2 hydrocarbons were studied. The experiment shows that methane decomposition can be divided into three periods as the reaction proceeds.In the first period, a large number of free radicals were formed. While in the last period, the formation of C2 hydrocarbons and the decrease of free radicals were observed. The time and conditions of methane decomposition and formation of C2 hydrocarbons are different.

  14. Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

    Science.gov (United States)

    Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

    Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

  15. Time sequenced heating of multiple layers in a hydrocarbon containing formation

    Science.gov (United States)

    Goldberg, Bernard; Hale, Arthur Herman; Miller, David Scott; Vinegar, Harold J.

    2009-12-22

    A method for treating a hydrocarbon containing formation may include providing heat to a first hydrocarbon layer in the formation from a first heater located in an opening in the formation. The opening and the first heater may have a horizontal or inclined portion located in the first hydrocarbon layer and at least one connecting portion extending between the horizontal or inclined portion and the surface. Isolation material is placed in the opening such that the isolation material partially isolates the layer in which the horizontal or inclined portion of the first heater is located. An additional horizontal or inclined opening portion that extends from at least one of the connecting portions of the opening is formed in a second hydrocarbon layer. A second heater to provide heat the second hydrocarbon formation is placed in the additional substantially horizontal opening portion.

  16. An Alternative Approach to Aldol Reactions: Gold-Catalyzed Formation of Boron Enolates from Alkynes

    OpenAIRE

    Korner, C; Starkov, P.; Sheppard, T. D.

    2010-01-01

    A new method for enolate generation via the gold-catalyzed addition of boronic acids to alkynes is reported. The formation of boron enolates from readily accessible ortho-alkynylbenzeneboronic acids proceeds rapidly with 2 mol % PPh3AuNTf2 at ambient temperature. The enolates undergo aldol reaction with an aldehyde present in the reaction mixture to give cyclic boronate esters, which can be subsequently transformed into phenols, biaryls, or dihydrobenzofurans via oxidation, Suzuki-Miyaura, or...

  17. Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates

    OpenAIRE

    Lu, Zhou; Ohshita, Joji; Mizumo, Tomonobu

    2012-01-01

    Polysiloxanes are useful materials because of their functionality, such as high thermal stability, electrical resistance, and hydrophobicity. In this regard, we studied palladium-catalyzed formation of iodo-and bromopolysiloxanes from two types of hydrosiloxanes, alpha,omega-dihydropoly(dimethylsiloxane) (1) and cyclotetra(hydromethylsiloxane) (2), and their reactions. Treatment of 1 with mixtures of cyclic ethers or lactones and MeI or allylBr in the presence of a catalytic amount of PdCl2 g...

  18. Solution mining dawsonite from hydrocarbon containing formations with a chelating agent

    Science.gov (United States)

    Vinegar, Harold J.

    2009-07-07

    A method for treating an oil shale formation comprising dawsonite includes providing heat from one or more heaters to the formation to heat the formation. Hydrocarbon fluids are produced from the formation. At least some dawsonite in the formation is decomposed with the provided heat. A chelating agent is provided to the formation to dissolve at least some dawsonite decomposition products. The dissolved dawsonite decomposition products are produced from the formation.

  19. 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.

  20. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis.

    Science.gov (United States)

    Lin, Shuangjun; Van Lanen, Steven G; Shen, Ben

    2009-03-17

    Nonribosomal peptide synthetases (NRPSs) catalyze the biosynthesis of many biologically active peptides and typically are modular, with each extension module minimally consisting of a condensation, an adenylation, and a peptidyl carrier protein domain responsible for incorporation of an amino acid into the growing peptide chain. C-1027 is a chromoprotein antitumor antibiotic whose enediyne chromophore consists of an enediyne core, a deoxy aminosugar, a benzoxazolinate, and a beta-amino acid moiety. Bioinformatics analysis suggested that the activation and incorporation of the beta-amino acid moiety into C-1027 follows an NRPS mechanism whereby biosynthetic intermediates are tethered to the peptidyl carrier protein SgcC2. Here, we report the biochemical characterization of SgcC5, an NRPS condensation enzyme that catalyzes ester bond formation between the SgcC2-tethered (S)-3-chloro-5-hydroxy-beta-tyrosine and (R)-1-phenyl-1,2-ethanediol, a mimic of the enediyne core. SgcC5 uses (S)-3-chloro-5-hydroxy-beta-tyrosyl-SgcC2 as the donor substrate and exhibits regiospecificity for the C-2 hydroxyl group of the enediyne core mimic as the acceptor substrate. Remarkably, SgcC5 is also capable of catalyzing amide bond formation, albeit with significantly reduced efficiency, between (S)-3-chloro-5-hydroxy-beta-tyrosyl-(S)-SgcC2 and (R)-2-amino-1-phenyl-1-ethanol, an alternative enediyne core mimic bearing an amine at its C-2 position. Thus, SgcC5 is capable of catalyzing both ester and amide bond formation, providing an evolutionary link between amide- and ester-forming condensation enzymes. PMID:19246381

  1. In situ recovery from residually heated sections in a hydrocarbon containing formation

    Science.gov (United States)

    Vinegar, Harold J.; Karanikas, John Michael; Ryan, Robert Charles

    2010-12-14

    Methods of treating a tar sands formation is described herein. The methods may include providing heat to a first section of a hydrocarbon layer in the formation from a plurality of heaters located in the first section of the formation. Heat is transferred from the heaters so that at least a first section of the formation reaches a selected temperature. At least a portion of residual heat from the first section transfers from the first section to a second section of the formation. At least a portion of hydrocarbons in the second section are mobilized by providing a solvation fluid and/or a pressurizing fluid to the second section of the formation.

  2. Oxidation of saturated hydrocarbons with peroxyacetic acid catalyzed by vanadium complexes

    OpenAIRE

    Gonzalez Cuervo, Laura; Kozlov, Yuriy N.; Süss-Fink, Georg; Shul’pin, Georgiy B.

    2009-01-01

    Peroxyacetic acid (PAA) oxidizes alkanes in acetonitrile or acetic acid at 60 °C if a soluble vanadium(V) salt, n-Bu4NVO3 (1), is used as a catalyst. Corresponding ketones, alcohols and alkyl hydroperoxides are the main products. Methane, ethane, propane, cyclohexane, and other higher alkanes were substrates in the oxidations. The proposed mechanism involves the formation of a complex between (1) and PAA with equilibrium constants 3.3 and 6.8 dm3 mol−1 for acetonitrile and acetic acid as solv...

  3. PCDD/F formation in an iron/potassium-catalyzed diesel particle filter.

    Science.gov (United States)

    Heeb, Norbert V; Zennegg, Markus; Haag, Regula; Wichser, Adrian; Schmid, Peter; Seiler, Cornelia; Ulrich, Andrea; Honegger, Peter; Zeyer, Kerstin; Emmenegger, Lukas; Bonsack, Peter; Zimmerli, Yan; Czerwinski, Jan; Kasper, Markus; Mayer, Andreas

    2013-06-18

    Catalytic diesel particle filters (DPFs) have evolved to a powerful environmental technology. Several metal-based, fuel soluble catalysts, so-called fuel-borne catalysts (FBCs), were developed to catalyze soot combustion and support filter regeneration. Mainly iron- and cerium-based FBCs have been commercialized for passenger cars and heavy-duty vehicle applications. We investigated a new iron/potassium-based FBC used in combination with an uncoated silicon carbide filter and report effects on emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs). The PCDD/F formation potential was assessed under best and worst case conditions, as required for filter approval under the VERT protocol. TEQ-weighted PCDD/F emissions remained low when using the Fe/K catalyst (37/7.5 μg/g) with the filter and commercial, low-sulfur fuel. The addition of chlorine (10 μg/g) immediately led to an intense PCDD/F formation in the Fe/K-DPF. TEQ-based emissions increased 51-fold from engine-out levels of 95 to 4800 pg I-TEQ/L after the DPF. Emissions of 2,3,7,8-TCDD, the most toxic congener (TEF = 1.0), increased 320-fold, those of 2,3,7,8-TCDF (TEF = 0.1) even 540-fold. Remarkable pattern changes were noticed, indicating a preferential formation of tetrachlorinated dibenzofurans. It has been shown that potassium acts as a structural promoter inducing the formation of magnetite (Fe3O4) rather than hematite (Fe2O3). This may alter the catalytic properties of iron. But the chemical nature of this new catalyst is yet unknown, and we are far from an established mechanism for this new pathway to PCDD/Fs. In conclusion, the iron/potassium-catalyzed DPF has a high PCDD/F formation potential, similar to the ones of copper-catalyzed filters, the latter are prohibited by Swiss legislation. PMID:23713673

  4. Condensation reaction of formaldehyde and methyl formate catalyzed by a composite catalyst system

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The condensation reaction of formaldehyde and methyl formate to form methyl glycolate and methyl methoxy acetate catalyzed by p-toluenesulfonic acid and different Lewis acid compounds has been investigated. The composite catalytic system consisting of p-toluenesulfonic acid and NiX2 (X = Cl, Br, I), especially NiI2, exhibited a high catalytic performance for the condensation reaction, the total yield of MG and MMAc was up to 72.37%.(C) 2007 Gong Ying Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

  5. Methane formation from CaCO3 reduction catalyzed by high pressure

    Institute of Scientific and Technical Information of China (English)

    Jin Yang Chen; Lu Jiang Jin; Jun Ping Dong; Hai Fei Zheng; Gui Yang Liu

    2008-01-01

    Under high pressures of several giga-pascals using hydrothermal diamond anvil cell,methane generated directly from CaCO3 reduction in gold-lined chamber is in situ measured by Raman spectroscopy at the temperature of 550 ℃.The reducing agents include FeO,SiO and natural fayalite (Fe2SiO4),and the resource of hydrogen are water and natural serpentine (Mg3Si2O5(OH)4).The study demonstrates the existence of abiogenic formation of methane under high pressures in the Earth's interior and that the application of high pressure to catalyze multicomponent reactions is a very promising method.

  6. Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Poreddy, Raju; Engelbrekt, Christian;

    2014-01-01

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions...... production of H-2 in the gas phase. The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by...

  7. Characteristics of hydrocarbon sources and controlling factors of their formation in Pingliang Formation, West Ordos Basin

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    According to organic geochemistry and organic petrology, the hydrocarbon sources in Pingliang Formation, W. Ordos basin, are systematically evaluated. The organic abundance of hydrocarbon source in this research is higher in the upper part of profiles than In the low, and more in mudstone than in carbonate. Most of organic matters become sapropelic, and few are humlc-aapropelic in the regions of Shibangou and Zhuzisan. According to stable isotopes of carbon and oxygen in carbonate rock, boron index and ratios of elements, palaeo-salinity and sedimentary velocity are calculated. The two factors of paleao-salinity and sediment velocity, which control the distribution of organic matters, are discussed.Good relationship is found between water salinity and abundance of organic matter; in contrast, poor correlation is observed between salinity and types of organic matters. The relative sediment velocity in the research regions is also related with organic abundance and types. A low sediment velocity would lead to high abundance and good type of organic matters, and vice versa.

  8. Investigation on Methane Decomposition and the Formation of C2 Hydrocarbons in DC Discharge Plasma byEmission Spectroscopy

    Institute of Scientific and Technical Information of China (English)

    贺建勋; 韩媛媛; 高爱华; 周引穗; 陆治国

    2004-01-01

    The IR emission spectra of methane were measured under DC glow discharge conditions. The distinct difference in time between methane decomposition and C2 hydrocarbons formation was specially pointed out. C2 hydrocarbons formed at the end of methane decomposition. The optimum condition for C2 hydrocarbon formation was studied and the optimum combination between electric current density and methane input quantity was suggested. The appropriate reaction conditions for methane decomposition and C2 hydrocarbons formation are different, so high yield of C2 hydrocarbons will be probably obtained when different conditions are taken.

  9. X-ray photoelectron spectroscopy study of catalyzed aluminum carbide formation at aluminum-carbon interfaces

    Science.gov (United States)

    Rabenberg, L.; Maruyama, Benji

    1990-01-01

    Aluminum carbide may form at aluminum-graphite interfaces during the high-temperature processing of graphite fiber-reinforced aluminum metal matrix composites. The chemical interactions leading to the formation of the aluminum carbide in the solid state involve the breaking of the carbon-carbon bonds within the graphite, the transport of the carbon atoms across the interface, and the reaction with the aluminum to form Al4C3. The aluminum carbide formation process has been followed using X-ray photoelectron spectroscopy of model, thin-film, reaction couples. The overall reaction is shown to be catalyzed by the presence of water vapor. Water at the interface increases reaction kinetics by apparently weakening the bonds between the surface carbon atoms and their substrate. This result is in general agreement with what is known to occur during the oxidation of graphite in air.

  10. Phosphoserine Lyase Deoxyribozymes: DNA-Catalyzed Formation of Dehydroalanine Residues in Peptides.

    Science.gov (United States)

    Chandrasekar, Jagadeeswaran; Wylder, Adam C; Silverman, Scott K

    2015-08-01

    Dehydroalanine (Dha) is a nonproteinogenic electrophilic amino acid that is a synthetic intermediate or product in the biosynthesis of several bioactive cyclic peptides such as lantibiotics, thiopeptides, and microcystins. Dha also enables labeling of proteins and synthesis of post-translationally modified proteins and their analogues. However, current chemical approaches to introducing Dha into peptides have substantial limitations. Using in vitro selection, here we show that DNA can catalyze Zn(2+) or Zn(2+)/Mn(2+)-dependent formation of Dha from phosphoserine (pSer), i.e., exhibit pSer lyase activity, a fundamentally new DNA-catalyzed reaction. Two new pSer lyase deoxyribozymes, named Dha-forming deoxyribozymes 1 and 2 (DhaDz1 and DhaDz2), each function with multiple turnover on the model hexapeptide substrate that was used during selection. Using DhaDz1, we generated Dha from pSer within an unrelated linear 13-mer peptide. Subsequent base-promoted intramolecular cyclization of homocysteine into Dha formed a stable cystathionine (thioether) analogue of the complement inhibitor compstatin. These findings establish the fundamental catalytic ability of DNA to eliminate phosphate from pSer to form Dha and suggest that with further development, pSer lyase deoxyribozymes will have broad practical utility for site-specific enzymatic synthesis of Dha from pSer in peptide substrates. PMID:26200899

  11. Formation and emission of large furans and oxygenated hydrocarbons from flames.

    Science.gov (United States)

    Johansson, K Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F; Schrader, Paul E; Popolan-Vaida, Denisia M; Richards-Henderson, Nicole K; Wilson, Kevin R; Violi, Angela; Michelsen, Hope A

    2016-07-26

    Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming. PMID:27410045

  12. Formation Dynamics and Quantitative Prediction of Hydrocarbons of the Superpressure System in the Dongying Sag

    Institute of Scientific and Technical Information of China (English)

    SUI Fenggui; HAO Xuefeng; LIU Qing; ZHUO Qingong; ZHANG Shouchun

    2008-01-01

    Based on the theory of formation dynamics of oil/gas pools, the Dongying sag can be divided into three dynamic systems regarding the accumulation of oil and gas: the superpressure closed system,the semi-closed system and the normal pressure open system. Based on the analysis of genesis of superpressure in the superpressure closed system and the rule of hydrocarbon expulsion,it is found that hydrocarbon generation is related to superpressure, which is the main driving factor of hydrocarbon migration. Micro fractures formed by superpressure are the main channels for hydrocarbon migration. There are three dynamic patterns for hydrocarbon expulsion: free water drainage, hydrocarbon accumulation and drainage through micro fissures. In the superpressure closed system, the oil-driving-water process and oil/gas accumulation were completed in lithologic traps by way of such two dynamic patterns as episodic evolution of superpressure systems and episodic pressure release of faults. The oil-bearing capacity of lithologic traps is intimately related to reservoir-forming dynamic force. Quantitative evaluation of dynamic conditions for pool formation can effectively predict the oil-bearing capability of traps.

  13. Formation of magnetic minerals at hydrocarbon-generation conditions

    OpenAIRE

    Abubakar, R.; Muxworthy, A. R.; Sephton, M.A.; Southern, P.; Watson, J. S.; Fraser, A.J.; Almeida, T.P.

    2015-01-01

    In this paper, we report the pyrolysis and formation of magnetic minerals in three source rock samples from the Wessex Basin in Dorset, southern England. The experimental conditions in the laboratory recreated the catagenesis environment of oil source rocks. Magnetic analysis of both the heated and the unheated samples at room temperature and at very low-temperatures (5 K), coupled with transmission electron-microscopy imaging and X-ray analysis, revealed the formation of nanometre-sized (...

  14. Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

    OpenAIRE

    Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker III, D. R.

    2016-01-01

    Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO  >  10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systemat...

  15. Kinetics of Hydrocarbon formation in a- C:H Film deposition plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Cal, E. de la; Tabares, F. L.

    1993-07-01

    The formation of C2 and Cp hydrocarbons during the PACVD of a-C:H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanisms of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene formation was found to be directly related to the formation of the film on top of the carburized metal. (Author) 12 refs.

  16. EXPERIMENTAL EVIDENCE FOR THE FORMATION OF HIGHLY SUPERHYDROGENATED POLYCYCLIC AROMATIC HYDROCARBONS THROUGH H ATOM ADDITION AND THEIR CATALYTIC ROLE IN H2 FORMATION

    DEFF Research Database (Denmark)

    Thrower, John; Jørgensen, Bjarke; Friis, Emil Enderup; Baouche, Saoud; Luntz, Alan C.; Andersen, Mie; Hammer, Bjørk; Hornekær, Liv

    2012-01-01

    Mass spectrometry measurements show the formation of highly superhydrogenated derivatives of the polycyclic aromatic hydrocarbon molecule coronene through H atom addition reactions. The observed product mass distribution provides evidence also for abstraction reactions resulting in H2 formation, ...

  17. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  18. ROLE OF COPPER,ZINC-SUPEROXIDE DISMUTASE IN CATALYZING NITROTYROSINE FORMATION IN MURINE LIVER

    Science.gov (United States)

    The solely known function of Cu,Zn-superoxide dismutase (SOD1) is to catalyze the dismutation of superoxide anion into hydrogen peroxide. Our objective was to determine if SOD1 catalyzed murine liver protein nitration induced by acetaminophen (APAP) and lipopolysaccharide (LPS). Liver and plasma ...

  19. Methanogenic degradation of petroleum hydrocarbons in subsurface environments remediation, heavy oil formation, and energy recovery.

    Science.gov (United States)

    Gray, N D; Sherry, A; Hubert, C; Dolfing, J; Head, I M

    2010-01-01

    Hydrocarbons are common constituents of surface, shallow, and deep-subsurface environments. Under anaerobic conditions, hydrocarbons can be degraded to methane by methanogenic microbial consortia. This degradation process is widespread in the geosphere. In comparison with other anaerobic processes, methanogenic hydrocarbon degradation is more sustainable over geological time scales because replenishment of an exogenous electron acceptor is not required. As a consequence, this process has been responsible for the formation of the world's vast deposits of heavy oil, which far exceed conventional oil assets such as those found in the Middle East. Methanogenic degradation is also a potentially important component of attenuation in hydrocarbon contamination plumes. Studies of the organisms, syntrophic partnerships, mechanisms, and geochemical signatures associated with methanogenic hydrocarbon degradation have identified common themes and diagnostic markers for this process in the subsurface. These studies have also identified the potential to engineer methanogenic processes to enhance the recovery of energy assets as biogenic methane from residual oils stranded in petroleum systems. PMID:20602990

  20. Time-of-flight measurement of resonant molecular formation in muon catalyzed dt fusion

    International Nuclear Information System (INIS)

    Preliminary results are reported for an experiment at TRIUMF where a time-of-flight technique was tested for measuring the energy dependence of the rate for muon catalyzed dt fusion. Muonic tritium toms were created following transfer of negative muons from muonic protium in a layer of solid hydrogen (protium) containing a small fraction of tritium. The atoms escaped from the solid layer via the Ramsauer-Townsend mechanism, traversed a drift region of 18 mm, and then struck an adjacent layer of deuterium, where the muonic atom could form a molecular system. The time of detection of a fusion product (neutron or alpha) following muon arrival is dependent upon the energy of the muonic tritium atom as it traverses the drift region. By comparison of the time distribution of fusion events with a prediction based on the theoretical energy dependence of the rate, the strength of resonant formation can in principle be determined. The results extracted so far are discussed and the limitations of the method are examined

  1. Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

    Directory of Open Access Journals (Sweden)

    Sultan Taskaya

    2015-05-01

    Full Text Available Various N-propargylpyrrole and indolecarboxylic acids were efficiently converted into 3,4-dihydropyrrolo- and indolo-oxazin-1-one derivatives by a gold(III-catalyzed cyclization reaction. Some of the products underwent TFA-catalyzed double bond isomerization and some did not. Cyclization reactions in the presence of alcohol catalyzed by Au(I resulted in the formation of hemiacetals after cascade reactions.

  2. Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

    OpenAIRE

    Sultan Taskaya; Nurettin Menges; Metin Balci

    2015-01-01

    Various N-propargylpyrrole and indolecarboxylic acids were efficiently converted into 3,4-dihydropyrrolo- and indolo-oxazin-1-one derivatives by a gold(III)-catalyzed cyclization reaction. Some of the products underwent TFA-catalyzed double bond isomerization and some did not. Cyclization reactions in the presence of alcohol catalyzed by Au(I) resulted in the formation of hemiacetals after cascade reactions.

  3. Tryptophan Oxidative Metabolism Catalyzed by Geobacillus Stearothermophilus: A Thermophile Isolated from Kuwait Soil Contaminated with Petroleum Hydrocarbons

    OpenAIRE

    Al-Hassan, Jassim M.; Samira Al-Awadi; Sosamma Oommen; Abdulaziz Alkhamis; Mohammad Afzal

    2011-01-01

    Tryptophan metabolism has been extensively studied in humans as well as in soil. Its metabolism takes place mainly through kynurenine pathway yielding hydroxylated, deaminated and many other products of physiological significance. However, tryptophan metabolism has not been studied in an isolated thermophilic bacterium. Geobacillus stearothermophilus is a local thermophile isolated from Kuwait desert soil contaminated with petroleum hydrocarbons. The bacterium grows well at 65 °C in 0.05 M ph...

  4. NOx-Catalyzed Gas-Phase Activation of Methane:the Formation of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Chaoxian Xiao; Zhen Yan; Yuan Kou

    2003-01-01

    NOx-catalyzed oxidation of methane without a solid catalyst was investigated, and a hydrogen selectivity of 27% was obtained with an overall methane conversion of 34% and a free O2 concentration of 1.7% at 700 ℃.

  5. Phosphorus-carbon bond formation by lewis Acid catalyzed/mediated addition of silylphosphines.

    Science.gov (United States)

    Hayashi, Minoru; Matsuura, Yutaka; Nishimura, Yasunobu; Yamasaki, Toshikazu; Imai, Yoshito; Watanabe, Yutaka

    2007-09-28

    Triethylaluminum-catalyzed/mediated addition of a silylphosphine to aldehydes and epoxides is described. Organophosphines containing a silyloxy group at the alpha- or beta-position on the alkyl substituent are successfully prepared in good yields. PMID:17784776

  6. Synthetic and Mechanistic Studies on the Solvent-Dependent Copper-Catalyzed Formation of Indolizines and Chalcones

    OpenAIRE

    Albaladejo Maricó, María José; Alonso Valdés, Francisco; González Soria, María José

    2015-01-01

    Copper nanoparticles supported on activated carbon have been found to catalyze the multicomponent synthesis of indolizines from pyridine-2-carbaldehyde derivatives, secondary amines, and terminal alkynes in dichloromethane; in the absence of solvent, however, heterocyclic chalcones are formed. We provide compelling evidence that both processes take place through aldehyde–amine–alkyne coupling intermediates. In contrast to other well-known mechanisms for chalcone formation from aldehydes and a...

  7. Transition metal-catalyzed C(vinyl)-C(vinyl) bond formation via double C(vinyl)-H bond activation.

    Science.gov (United States)

    Shang, Xiaojie; Liu, Zhong-Quan

    2013-04-21

    Transition metal-catalyzed oxidative dehydrogenative coupling reactions of Caryl-H bonds with Cvinyl-H bonds to generate a Caryl-Cvinyl bonds have been well developed in recent decades. However, only a few studies have focused on the direct Cvinyl-Cvinyl bond formation via double Cvinyl-H bond activation. Recent developments in this active area have been highlighted in this tutorial review. PMID:23318664

  8. Lithological architecture, geological processes and energy-field environments are major factors for the formation of hydrocarbon reservoirs

    Institute of Scientific and Technical Information of China (English)

    ZHAO Wenzhi; WANG Zecheng; LI Xiaoqing; WANG Hongjun; WANG Zhaoyun

    2005-01-01

    The formation of hydrocarbon reservoirs is controlled by three major factors: lithological architecture, geological processes and energy-field environments. Among the three major factors, lithological architecture provides the storing medium for hydrocarbon; geological processes include hydrocarbon generation, migration, accumulation, preservation and modification; and energy-field environments refer to the various geothermal and geodynamic forces that affect the lithological architecture and drive the geological processes.In this study, we take Kela-2 and Sulige gas reservoirs as two examples to study relationships among the three major factors, and explain how these factors influence the scale and quality of hydrocarbon reservoirs.

  9. Kinetics of Hydrocarbon formation in a-C:H film deposition plasmas

    International Nuclear Information System (INIS)

    The formation of C2 and C3 hydrocarbons during the PACVD of a-C-H films from admixtures of methane with H2 and He has been investigated by mass spectrometry under several deposition condition. The time evolution of the observed species indicates that the formation mechanism of ethylene and acetylene are sensitive to the conditions of the wall during the growing of the film. Acetylene are sensitive to the conditions of the wall during the growing of the carburized metal. (Author)

  10. Predicting hydrocarbon potential of an earth formation underlying a body of water

    International Nuclear Information System (INIS)

    A method for the on-site collection and examination of small concentrations of methane dissolved in water so as to predict hydrocarbon potential of an earth formation underlying a body of water, said formation being a source of said methane, comprises: (i) sampling the water; (ii) continuously vacuum separating said water into liquid and gas phases; (iii) quantitatively separating interfering gas species from methane; (iv) quantitatively oxidising said methane; (v) cryogenically trapping the resulting gaseous carbon dioxide and water vapor at a trapping station, and (vi) isotopically examining said trapped carbon dioxide and water vapour for carbon and deuterium distribution. (author)

  11. Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2–H activation/C–O formation

    Directory of Open Access Journals (Sweden)

    Seohyun Shin

    2014-05-01

    Full Text Available We report an efficient Pd-catalyzed C(sp2–H activation/C–O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(arylarylphosphonic acid monoethyl esters under aerobic conditions.

  12. 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...

  13. Kinetics of allopregnanolone formation catalyzed by human 3 alpha-hydroxysteroid dehydrogenase type III (AKR1C2).

    Science.gov (United States)

    Trauger, John W; Jiang, Alice; Stearns, Brian A; LoGrasso, Philip V

    2002-11-12

    Allopregnanolone is a neurosteroid which exhibits anxiolytic and anticonvulsant activities through potentiation of the GABA(A) receptor. The reduction of 5alpha-dihydroprogesterone (5alpha-DHP), the last step in allopregnanolone biosynthesis, is catalyzed by 3alpha-hydroxysteroid dehydrogenases (3alpha-HSDs). While the mechanism of action of allopregnanolone and the physiological and pharmacological modulation of allopregnanolone concentrations in vivo have been extensively studied, there has been little characterization of the kinetics of human 3alpha-HSD catalyzed allopregnanolone formation. We report here determination of the kinetic mechanism for 5alpha-DHP reduction catalyzed by human 3alpha-HSD type III by using steady-state kinetics studies and assessment of the ability of fluoxetine and various other small molecules to activate 3alpha-HSD type III catalyzed allopregnanolone formation. Enzyme-catalyzed 5alpha-DHP reduction yielded two products, allopregnanolone and 5alpha,20alpha-tetrahydroprogesterone, as measured by using a radiometric thin-layer chromatography assay, while 5beta-DHP reduction yielded the neurosteroid pregnanolone as the only product. 5Beta-DHP reduction proceeded with a catalytic efficiency 10 times higher than that of 5alpha-DHP reduction. Two-substrate kinetic analysis and dead-end inhibition studies for 5alpha-DHP reduction and allopregnanolone oxidation indicated that 3alpha-HSD type III utilized a ternary complex (sequential) kinetic mechanism, with nicotinamide adenine dinucleotide cofactor binding before steroid substrate and leaving after steroid product. Since previous reports suggested that fluoxetine and certain other small molecules increased allopregnanolone concentrations in vivo by activating 3alpha-HSD type III, we investigated whether these small molecules were able to activate human 3alpha-HSD type III. Our results showed that, at concentrations up to 50 microM, fluoxetine, paroxetine, sertraline, norfluoxetine

  14. Large acceleration of α-chymotrypsin-catalyzed dipeptide formation by 18-crown-6 in organic solvents

    NARCIS (Netherlands)

    Unen, van Dirk-Jan; Engbersen, Johan F.J.; Reinhoudt, David N.

    1998-01-01

    The effects of 18-crown-6 on the synthesis of peptides catalyzed by α-chymotrypsin are reported. Lyophilization of the enzyme in the presence of 50 equivalents of 18-crown-6 results in a 425-fold enhanced activity when the reaction between the 2-chloroethylester of N-acetyl-L-phenylalanine and L-phe

  15. Formation of H{sub 2} from internally heated polycyclic aromatic hydrocarbons: Excitation energy dependence

    Energy Technology Data Exchange (ETDEWEB)

    Chen, T., E-mail: tao.chen@fysik.su.se, E-mail: henning@fysik.su.se; Gatchell, M.; Stockett, M. H.; Schmidt, H. T.; Cederquist, H.; Zettergren, H., E-mail: tao.chen@fysik.su.se, E-mail: henning@fysik.su.se [Department of Physics, Stockholm University, S-106 91 Stockholm (Sweden); Delaunay, R.; Rousseau, P.; Adoui, L. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Université de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); Université de Caen Basse-Normandie, Esplanade de la Paix, F-14032 Caen (France); Domaracka, A.; Huber, B. A. [CIMAP, UMR 6252, CEA/CNRS/ENSICAEN/Université de Caen Basse-Normandie, bd Henri Becquerel, BP 5133, F-14070 Caen cedex 05 (France); Micelotta, E. R. [Université Paris Sud, Institut d’Astrophysique Spatiale, UMR 8617, 91405 Orsay (France); Tielens, A. G. G. M. [Leiden Observatory, Leiden University, P.O. Box 9513, 2300 RA Leiden (Netherlands)

    2015-04-14

    We have investigated the effectiveness of molecular hydrogen (H{sub 2}) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H{sub 2} formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H{sub 2} emission is correlated with multi-fragmentation processes, which means that the [PAH-2H]{sup +} peak intensities in the mass spectra may not be used for estimating H{sub 2}-formation rates.

  16. Production of a New Emulsifier Material for the Formation Heavy Hydrocarbon/Water Emulsion

    Directory of Open Access Journals (Sweden)

    Afshin Farahbakhsh

    2011-04-01

    Full Text Available Emulsifiers are a unique class of compounds that have proved to have a variety of potential applications in formation of hydrocarbon in water emulsion, in enhancement of oil recovery and in the reduction of heavy oil viscosity. In this paper, a bio emulsifier was synthesized by a strain of Bacillus licheniformis and was separated by an autoclave and centrifugal process; the purification of bio emulsifier and the increase quality of product was done by adding sulfuric acid (H2SO4 (98% to the solution and centrifuging this compound again. This bio emulsifier has the property of emulsification to a wide range of heavy hydrocarbon to form a stable hydrocarbon-water emulsion. This bio emulsifier could reduce Iranian Nuroze high viscosity oil of about 10000 cP down to 250 cP. This means about 97% decreases in the viscosity. The emulsion stable this condition for 48 hr and the viscosity slowly increases to 4000cp until 192 hr. The stability of the oil in water emulsion during 48hr allows the heavy oil to be transported practically over lengthy distances or remain stable for long periods of time prior to utilization.

  17. LABORATORY INVESTIGATIONS OF POLYCYCLIC AROMATIC HYDROCARBON FORMATION AND DESTRUCTION IN THE CIRCUMSTELLAR OUTFLOWS OF CARBON STARS

    International Nuclear Information System (INIS)

    The formation and destruction mechanisms of interstellar dust analogs formed from a variety of polycyclic aromatic hydrocarbon (PAH) and hydrocarbon molecular precursors are studied in the laboratory. We used the newly developed facility COSmIC, which simulates interstellar and circumstellar environments, to investigate both PAHs and species that include the cosmically abundant atoms O, N, and S. The species generated in a discharge plasma are detected, monitored, and characterized in situ using highly sensitive techniques that provide both spectral and ion mass information. We report here the first series of measurements obtained in these experiments which focus on the characterization of the most efficient molecular precursors in the chemical pathways that eventually lead to the formation of carbonaceous grains in the stellar envelopes of carbon stars. We compare and discuss the relative efficiencies of the various molecular precursors that lead to the formation of the building blocks of carbon grains. We discuss the most probable molecular precursors in terms of size and structure and the implications for the expected growth and destruction processes of interstellar carbonaceous dust

  18. LABORATORY INVESTIGATIONS OF POLYCYCLIC AROMATIC HYDROCARBON FORMATION AND DESTRUCTION IN THE CIRCUMSTELLAR OUTFLOWS OF CARBON STARS

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Cesar S.; Salama, Farid, E-mail: cesar.contreras@nasa.gov, E-mail: Farid.Salama@nasa.gov [Space Science and Astrobiology Division, NASA-Ames Research Center, Moffett Field, CA 94035 (United States)

    2013-09-15

    The formation and destruction mechanisms of interstellar dust analogs formed from a variety of polycyclic aromatic hydrocarbon (PAH) and hydrocarbon molecular precursors are studied in the laboratory. We used the newly developed facility COSmIC, which simulates interstellar and circumstellar environments, to investigate both PAHs and species that include the cosmically abundant atoms O, N, and S. The species generated in a discharge plasma are detected, monitored, and characterized in situ using highly sensitive techniques that provide both spectral and ion mass information. We report here the first series of measurements obtained in these experiments which focus on the characterization of the most efficient molecular precursors in the chemical pathways that eventually lead to the formation of carbonaceous grains in the stellar envelopes of carbon stars. We compare and discuss the relative efficiencies of the various molecular precursors that lead to the formation of the building blocks of carbon grains. We discuss the most probable molecular precursors in terms of size and structure and the implications for the expected growth and destruction processes of interstellar carbonaceous dust.

  19. Production of a New Emulsifier Material for the Formation Heavy Hydrocarbon/Water Emulsion

    OpenAIRE

    Afshin Farahbakhsh; Majid Taghizadeh; Bagher Yakhchali; Kamyar Movagharnejad; Hassan Ali Zamani

    2011-01-01

    Emulsifiers are a unique class of compounds that have proved to have a variety of potential applications in formation of hydrocarbon in water emulsion, in enhancement of oil recovery and in the reduction of heavy oil viscosity. In this paper, a bio emulsifier was synthesized by a strain of Bacillus licheniformis and was separated by an autoclave and centrifugal process; the purification of bio emulsifier and the increase quality of product was done by adding sulfuric acid (H2SO4) (98%) to the...

  20. Formation of metal-ion adducts and evidence for surface-catalyzed ionization in electrospray analysis of pharmaceuticals and pesticides

    Science.gov (United States)

    Thurman, E.M.; Ferrer, I.

    2002-01-01

    The formation of metal ion adducts in liquid chromatography/mass spectrometry positive-ion electrospray analysis of pharmaceuticals and pesticides was investigated. The evidence of surface-catalyzed ionization in the electrospray analysis was also studied. Both positive and negative ion mass spectrometry were used for the analysis of the products. It was found that the sodium adducts formed in the analysis included single, double, and triple sodium adducts. Adduction was found to occur by attachment of the metal ion to carboxyl, carbonyl and aromatic pi electrons of the molecule.

  1. Solvent-Free Selective Condensations Based on the Formation of the Olefinic (C=C Bond Catalyzed by Organocatalyst

    Directory of Open Access Journals (Sweden)

    Heyuan Song

    2016-07-01

    Full Text Available Pyrrolidine and its derivatives were used to catalyze aldol and Knoevenagel condensations for the formation of the olefinic (C=C bond under solvent-free conditions. The 3-pyrrolidinamine showed high activity and afforded excellent yields of α,β-unsaturated compounds. The aldol condensation of aromatic/heterocyclic aldehydes with ketones affords enones in high conversion (99.5% and selectivity (92.7%. Good to excellent yields of α,β-unsaturated compounds were obtained in the Knoevenagel condensation of aldehydes with methylene-activated substrates.

  2. Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives

    OpenAIRE

    Song, Bingrui

    2013-01-01

    Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient ...

  3. Effects of oil and dispersant on formation of marine oil snow and transport of oil hydrocarbons.

    Science.gov (United States)

    Fu, Jie; Gong, Yanyan; Zhao, Xiao; O'Reilly, S E; Zhao, Dongye

    2014-12-16

    This work explored the formation mechanism of marine oil snow (MOS) and the associated transport of oil hydrocarbons in the presence of a stereotype oil dispersant, Corexit EC9500A. Roller table experiments were carried out to simulate natural marine processes that lead to formation of marine snow. We found that both oil and the dispersant greatly promoted the formation of MOS, and MOS flocs as large as 1.6-2.1 mm (mean diameter) were developed within 3-6 days. Natural suspended solids and indigenous microorganisms play critical roles in the MOS formation. The addition of oil and the dispersant greatly enhanced the bacterial growth and extracellular polymeric substance (EPS) content, resulting in increased flocculation and formation of MOS. The dispersant not only enhanced dissolution of n-alkanes (C9-C40) from oil slicks into the aqueous phase, but facilitated sorption of more oil components onto MOS. The incorporation of oil droplets in MOS resulted in a two-way (rising and sinking) transport of the MOS particles. More lower-molecular-weight (LMW) n-alkanes (C9-C18) were partitioned in MOS than in the aqueous phase in the presence of the dispersant. The information can aid in our understanding of dispersant effects on MOS formation and oil transport following an oil spill event. PMID:25420231

  4. Reservoir attributes of a hydrocarbon-prone sandstone complex: case of the Pab Formation (Late Cretaceous) of Southwest Pakistan

    DEFF Research Database (Denmark)

    Umar, Muhammad; Khan, Abdul Salam; Kelling, Gilbert;

    2016-01-01

    Links between the architectural elements of major sand bodies and reservoir attributes have been explored in a field study of the hydrocarbon-yielding Late Cretaceous Pab Formation of southwest Pakistan. The lithofacies and facies associations represented in the Pab Formation are the main...

  5. Apparatus for use in predicting hydrocarbon potential of an earth formation underlying a body of water

    International Nuclear Information System (INIS)

    In a relatively quick, convenient and highly accurate technique for the determination of a carbonaceous gas, normally methane, contained in water samples collected at depth from a body of water overlying an earth formation to predict the hydrocarbon-containing potential of the earth formation, carbonaceous gaseous constituents liberated from the water are carried via an air stream to flow into and through an isotope trapping network where collection in microlitre amounts occurs. The isotope capture apparatus comprises a box-like structure formed from a series of panel members, front panel member intersecting the bottom panel member near the centre of the latter and carrying interconnected gas trapping and stripping sections, the structure also comprising a detachable lid connectable by means, for protection of sections. (author)

  6. Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid, aluminum chloride, and hydrochloric acid

    Science.gov (United States)

    Tretinnikov, O. N.; Sushko, N. I.; Malyi, A. B.

    2016-07-01

    Formation of linear polyenes-(CH=CH)n-via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10-12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.

  7. Intracellular Copper Does Not Catalyze the Formation of Oxidative DNA Damage in Escherichia coli▿

    OpenAIRE

    Macomber, Lee; Rensing, Christopher; Imlay, James A.

    2006-01-01

    Because copper catalyzes the conversion of H2O2 to hydroxyl radicals in vitro, it has been proposed that oxidative DNA damage may be an important component of copper toxicity. Elimination of the copper export genes, copA, cueO, and cusCFBA, rendered Escherichia coli sensitive to growth inhibition by copper and provided forcing circumstances in which this hypothesis could be tested. When the cells were grown in medium supplemented with copper, the intracellular copper content increased 20-fold...

  8. An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric CC bond formation.

    Science.gov (United States)

    Negishi, Ei-Ichi; Tan, Ze; Liang, Bo; Novak, Tibor

    2004-04-20

    An efficient and general method for the synthesis of reduced polypropionates has been developed through the application of asymmetric carboalumination of alkenes catalyzed by dichlorobis(1-neomenthylindenyl)zirconium [(NMI)(2)ZrCl(2)]. In this investigation, attention has been focused on those reduced polypropionates that are alpha-monoheterofunctional and either omega-ethyl or omega-n-propyl. The reaction of 3-buten-1-ol with triethylaluminum (Et(3)Al) or tripropylaluminum ((n)Pr(3)Al) in the presence of (NMI)(2)ZrCl(2) and isobutylaluminoxane gave, after protonolysis, (R)-3-methyl-1-pentanol as well as (R)- and (S)-3-methyl-1-hexanols in 88-92% yield in 90-92% enantiomeric excess in one step. These 3-monomethyl-1-alkanols were then converted to two stereoisomers each of 2,4-dimethyl-1-hexanols and 2,4-dimethyl-1-heptanols via methylalumination catalyzed by (NMI)(2)ZrCl(2) and methylaluminoxane followed by oxidation with O(2). The four-step (or three-isolation-step) protocol provided syn-2,4-dimethyl-1-alkanols of >/=98% stereoisomeric purity in approximately 50% overall yields, whereas (2S,4R)-2,4-dimethyl-1-hexanol of comparable purity was obtained in 40% overall yield. Commercial availability of (S)-2-methyl-1-butanol as a relatively inexpensive material suggested its use in the synthesis of (2S,4S)- and (2R,4S)-2,4-dimethyl-1-hexanols via a three-step protocol consisting of (i) iodination, (ii) zincation followed by Pd-catalyzed vinylation, and (iii) Zr-catalyzed methylalumination followed by oxidation with O(2). This three-step protocol is iterative and applicable to the synthesis of reduced polypropionates containing three or more branching methyl groups, rendering this method for the synthesis of reduced polypropionates generally applicable. Its synthetic utility has been demonstrated by preparing the side chain of zaragozic acid A and the C11-C20 fragment of antibiotics TMC-151 A-F. PMID:15073327

  9. Authigenic carbonate formation at hydrocarbon seeps in continental margin sediments: A comparative study

    Science.gov (United States)

    Naehr, T.H.; Eichhubl, P.; Orphan, V.J.; Hovland, M.; Paull, C.K.; Ussler, W., III; Lorenson, T.D.; Greene, H. Gary

    2007-01-01

    Authigenic carbonates from five continental margin locations, the Eel River Basin, Monterey Bay, Santa Barbara Basin, the Sea of Okhotsk, and the North Sea, exhibit a wide range of mineralogical and stable isotopic compositions. These precipitates include aragonite, low- and high-Mg calcite, and dolomite. The carbon isotopic composition of carbonates varies widely, ranging from -60??? to +26???, indicating complex carbon sources that include 13C-depleted microbial and thermogenic methane and residual, 13C-enriched, bicarbonate. A similarly large variability of ??18O values (-5.5??? to +8.9???) demonstrates the geochemical complexity of these sites, with some samples pointing toward an 18O-enriched oxygen source possibly related to advection of 18O-enriched formation water or to the decomposition of gas hydrate. Samples depleted in 18O are consistent with formation deeper in the sediment or mixing of pore fluids with meteoric water during carbonate precipitation. A wide range of isotopic and mineralogical variation in authigenic carbonate composition within individual study areas but common trends across multiple geographic areas suggest that these parameters alone are not indicative for certain tectonic or geochemical settings. Rather, the observed variations probably reflect local controls on the flux of carbon and other reduced ions, such as faults, fluid conduits, the presence or absence of gas hydrate in the sediment, and the temporal evolution of the local carbon reservoir. Areas with seafloor carbonates that indicate formation at greater depth below the sediment-water interface must have undergone uplift and erosion in the past or are still being uplifted. Consequently, the occurrence of carbonate slabs on the seafloor in areas of active hydrocarbon seepage is commonly an indicator of exhumation following carbonate precipitation in the shallow subsurface. Therefore, careful petrographic and geochemical analyses are critical components necessary for the

  10. Polycyclic aromatic hydrocarbon (PAH) formation from benzyl radicals: a reaction kinetics study.

    Science.gov (United States)

    Sinha, Sourab; Raj, Abhijeet

    2016-03-01

    The role of resonantly stabilized radicals such as propargyl, cyclopentadienyl and benzyl in the formation of aromatic hydrocarbons such as benzene and naphthalene in the high temperature environments has been long known. In this work, the possibility of benzyl recombination to form three-ring aromatics, phenanthrene and anthracene, is explored. A reaction mechanism for it is developed, where reaction energetics are calculated using density functional theory (B3LYP functional with 6-311++G(d,p) basis set) and CBS-QB3, while temperature-dependent reaction kinetics are evaluated using transition state theory. The mechanism begins with barrierless formation of bibenzyl from two benzyl radicals with the release of 283.2 kJ mol(-1) of reaction energy. The further reactions involve H-abstraction by a H atom, H-desorption, H-migration, and ring closure to gain aromaticity. Through mechanism and rate of production analyses, the important reactions leading to phenanthrene and anthracene formation are determined. Phenanthrene is found to be the major product at high temperatures. Premixed laminar flame simulations are carried out by including the proposed reactions for phenanthrene formation from benzyl radicals and compared to experimentally observed species profiles to understand their effects on species concentrations. PMID:26923612

  11. Effects of Large Polycyclic Aromatic Hydrocarbons on the Soot Formation in Ethylene-Air Nonpremixed Flames

    KAUST Repository

    Prabhu, S.

    2015-03-30

    This study presents updated comprehensive gas-phase kinetic mechanism and aerosol models to predict soot formation characteristics in ethylene-air nonpremixed flames. A main objective is to investigate the sensitivity of the soot formation rate to various chemical pathways for large polycyclic aromatic hydrocarbons (PAH). In this study, the detailed chemical mechanism was reduced from 397 to 99 species using directed relation graph (DRG) and sensitivity analysis. The method of moments with interpolative closure (MOMIC) was employed for the soot aerosol model. Counterflow nonpremixed flames of pure ethylene at low strain rate sooting conditions are considered, for which the sensitivity of soot formation characteristics with respect to hetrogeneous nucleation is investigated. Results show that higher PAH concentrations result in higher soot nucleation rate, and that the average size of the particles are in good agreement with experimental results. It is found that the nucleation processes (i.e., soot inception) from higher PAH precursors, coronene in particular, is critical for accurate prediction of the overall soot formation.

  12. A study of carbon formation and prevention in hydrocarbon-fueled SOFC

    Science.gov (United States)

    Kim, T.; Liu, G.; Boaro, M.; Lee, S.-I.; Vohs, J. M.; Gorte, R. J.; Al-Madhi, O. H.; Dabbousi, B. O.

    The formation and removal of the carbonaceous deposits formed by n-butane and liquid hydrocarbons, such as n-decane and proprietary light and heavy naphthas, between 973 and 1073 K on YSZ and ceria-YSZ, has been studied to determine conditions for stable operation of direct-utilization SOFC. First, it is shown that deactivation of SOFC with Cu-ceria-YSZ anodes operating on undiluted n-decane, a mixture of 80% n-decane and 20% toluene, or light naphtha at temperatures above 973 K is due to filling of the pores with polyaromatic compounds formed by gas-phase, free-radical reactions. Formation of these compounds occurs at a negligible rate below 973 K but increases rapidly above this temperature. The rate of formation also depends on the residence time of the fuel in the anode compartment. Because steam does not participate in the gas-phase reactions, carbonaceous deposits could form even at a H 2O:C ratio of 1.5, a value greater than the stability threshold predicted by thermodynamic calculations. Temperature programmed oxidation (TPO) measurements with 20% H 2O in He demonstrated that carbon deposits formed in pure YSZ were unreactive below 1073 K, while deposits formed on ceria-YSZ could be removed at temperatures as low as 923 K. Based on these results, we discuss strategies for avoiding carbon formation during the operation of direct-utilization anodes on oil-based liquid fuels.

  13. Hydrocarbon potential evaluation of the source rocks from the Abu Gabra Formation in the Sufyan Sag, Muglad Basin, Sudan

    Science.gov (United States)

    Qiao, Jinqi; Liu, Luofu; An, Fuli; Xiao, Fei; Wang, Ying; Wu, Kangjun; Zhao, Yuanyuan

    2016-06-01

    The Sufyan Sag is one of the low-exploration areas in the Muglad Basin (Sudan), and hydrocarbon potential evaluation of source rocks is the basis for its further exploration. The Abu Gabra Formation consisting of three members (AG3, AG2 and AG1 from bottom to top) was thought to be the main source rock formation, but detailed studies on its petroleum geology and geochemical characteristics are still insufficient. Through systematic analysis on distribution, organic matter abundance, organic matter type, organic matter maturity and characteristics of hydrocarbon generation and expulsion of the source rocks from the Abu Gabra Formation, the main source rock members were determined and the petroleum resource extent was estimated in the study area. The results show that dark mudstones are the thickest in the AG2 member while the thinnest in the AG1 member, and the thickness of the AG3 dark mudstone is not small either. The AG3 member have developed good-excellent source rock mainly with Type I kerogen. In the Southern Sub-sag, the AG3 source rock began to generate hydrocarbons in the middle period of Bentiu. In the early period of Darfur, it reached the hydrocarbon generation and expulsion peak. It is in late mature stage currently. The AG2 member developed good-excellent source rock mainly with Types II1 and I kerogen, and has lower organic matter abundance than the AG3 member. In the Southern Sub-sag, the AG2 source rock began to generate hydrocarbons in the late period of Bentiu. In the late period of Darfur, it reached the peak of hydrocarbon generation and its expulsion. It is in middle mature stage currently. The AG1 member developed fair-good source rock mainly with Types II and III kerogen. Throughout the geological evolution history, the AG1 source rock has no effective hydrocarbon generation or expulsion processes. Combined with basin modeling results, we have concluded that the AG3 and AG2 members are the main source rock layers and the Southern Sub-sag is

  14. Hydrocarbon migration and accumulation in the Upper Cretaceous Qingshankou Formation, Changling Sag, southern Songliao Basin: Insights from integrated analyses of fluid inclusion, oil source correlation and basin modelling

    Science.gov (United States)

    Dong, Tian; He, Sheng; Wang, Dexi; Hou, Yuguang

    2014-08-01

    The Upper Cretaceous Qingshankou Formation acts as both the source and reservoir sequence in the Changling Sag, situated in the southern end of the Songliao Basin, northeast China. An integrated approach involving determination of hydrocarbon charging history, oil source correlation and hydrocarbon generation dynamic modeling was used to investigate hydrocarbon migration processes and further predict the favorable targets of hydrocarbon accumulations in the Qingshankou Formation. The hydrocarbon generation and charge history was investigated using fluid inclusion analysis, in combination with stratigraphic burial and thermal modeling. The source rocks began to generate hydrocarbons at around 82 Ma and the hydrocarbon charge event occurred from approximately 78 Ma to the end of Cretaceous (65.5 Ma) when a large tectonic uplift took place. Correlation of stable carbon isotopes of oils and extracts of source rocks indicates that oil was generated mainly from the first member of Qingshankou Formation (K2qn1), suggesting that hydrocarbon may have migrated vertically. Three dimensional (3D) petroleum system modeling was used to evaluate the processes of secondary hydrocarbon migration in the Qingshankou Formation since the latest Cretaceous. During the Late Cretaceous, hydrocarbon, mainly originated from the Qianan depression, migrated laterally to adjacent structural highs. Subsequent tectonic inversion, defined as the late Yanshan Orogeny, significantly changed hydrocarbon migration patterns, probably causing redistribution of primary hydrocarbon reservoirs. In the Tertiary, the Heidimiao depression was buried much deeper than the Qianan depression and became the main source kitchen. Hydrocarbon migration was primarily controlled by fluid potential and generally migrated from relatively high potential areas to low potential areas. Structural highs and lithologic transitions are potential traps for current oil and gas exploration. Finally, several preferred hydrocarbon

  15. The Potential of Eocene Shale of Nanggulan Formation as a Hydrocarbon Source Rock

    Directory of Open Access Journals (Sweden)

    S. Winardi

    2014-07-01

    Full Text Available DOI: 10.17014/ijog.v8i1.152In western Indonesia, Eocene shale is generally considered as a potential source rock. The Nanggulan Formation outcropping at Kulonprogo Yogyakarta consists of a shale interval of Eocene in age. Analysis of its organic material content, kerogen type, and maturity level were conducted to know its potential. The laboratory analysis of eleven samples were done to measure its TOC content. Samples with TOC > 0.5% then were analyzed to measure its Rv and TAI. Maturity level was also calculated by TTI from burial history model. The result of analysis shows there are various TOC contents and seven samples of them are categorized into a good-excellent class (TOC > 1%. Kerogen content of those samples is type III (non fluorescene amorphous-humic kerogen. One sample has a good indication of hydrocarbon formation (PY = 9.0 mg HC/g rock. Unfortunately thermal maturity level of the samples is immature (highest Rv 0.39, Tmax 422oC, and TAI 2. Otherwise, TTI calculation result from subsurface burial history modelling indicates that some areas are mature having reached gas window since 0.4 mya, especially in the area which had been influenced by a volcanic intrusion at Oligocene (28.5 mya. Therefore, the Nanggulan Formation shale has a potential capacity as a source rock with some limitation in maturity level.

  16. Measurement of non-methane hydrocarbons in Taipei city and their impact on ozone formation in relation to air quality.

    Science.gov (United States)

    Wu, Ben-Zen; Chang, Chih-Chung; Sree, Usha; Chiu, Konghwa; Lo, Jiunn-Guang

    2006-08-18

    Air pollutants data from semi-continuous measurements at multiple sampling sites in Taipei metropolitan area of Taiwan was obtained by collecting air samples in canisters. The hydrocarbon composition was determined by using GC/MS and GC/FID. The air samples were pre-concentrated onto glass beads prior to separation by PLOT and DB-1 columns of GC. The method showed detection limit of NO2 were measured by UV-differential optical absorption spectroscopy (UV-DOAS), and were utilized to determine the relative importance of non-methane hydrocarbons (NMHC) and significant contribution of NO2 in limiting ozone formation. The obtained results suggest that ozone formation in Taipei city is probably limited by the supply of non-methane hydrocarbons. The concentration profile of targeted pollutants was compared to other metropolitan areas to determine air quality and the pollutant sources. PMID:17723619

  17. Kinetic modeling of polycyclic aromatic hydrocarbons formation process for gasoline surrogate fuels

    International Nuclear Information System (INIS)

    Highlights: • A gasoline surrogate fuels mechanism with PAHs formation has been developed. • Validation including ignition delays and laminar flame speeds for gasoline. • Sensitivity analysis and rate of production analysis were performed. • Key species profiles and PAHs profiles could be predicted by this mechanism. - Abstract: It is very necessary to develop a comprehensive gasoline surrogate fuel chemical kinetic model that could accurately predict soot emissions and polycyclic aromatic hydrocarbons (PAHs) formation in internal combustion engines. Based on the consideration, this paper presents a toluene reference fuel (TRF) chemical mechanism to predict the PAHs formation process. This mechanism has been validated for ignition delays over a range of initial conditions covering the pressures from 15 to 60 bar, equivalence ratios from 0.5 to 2.0 and temperatures from 750 to 1280 K, especially for gasoline/air and two TRFs/air mixtures under engines conditions. Laminar flame speeds were also validated at low and high pressures. Furthermore, in order to guarantee the prediction accuracy of PAHs, premixed and opposed flow flames were simulated to validate the formation of PAHs and good agreements were obtained. Sensitivity analysis was performed to analyze the contribution of reactions to ignition delays and laminar flame speeds. Rate of production analysis was also carried out to identify the formation and consumption reaction pathways of A1 under different temperatures. The results indicated that the TRF–PAHs chemical mechanism could meet the demand of the PAHs simulation in engines. The proposed mechanism, which includes 219 species and 1229 reactions, is available as supporting Information for this article

  18. Oxygenation of saturated and unsaturated hydrocarbons with sodium periodate catalyzed by manganese(III) tetra-arylporphyrins, to study the axial ligation of imidazole

    Indian Academy of Sciences (India)

    Reza Tayebee

    2006-09-01

    Competitive oxygenation of cyclooctene and tetralin with sodium periodate catalyzed by MnIII(TPP)OAc, TPP = meso-tetraphenylporphyrin; MnIII (TNP)OAc, TNP = meso-tetrakis(1-naphthyl) porphyrin; MnIII (TMP)OAc, TMP = meso-tetrakis(2,4,6-trimethyl-phenyl)porphyrin; MnIII (TDCPP)OAc, TDCPP = meso-tetrakis(2,6-dichlorophenyl) porphyrin, and MnIII (TPNMe2-TFPP)OAc, TPNMe2-TFPP = meso-tetrakis(para-NMe2-tetrafluorophenyl)porphyrin, was carried out in the presence or absence of imidazole. This study showed that, in the absence of imidazole, selectivity for epoxide formation was high with electron-rich catalysts such as Mn(TPP)OAc, Mn(TNP)OAc and Mn(TMP)OAc, but low with electron-deficient catalysts such as Mn(TDCPP)OAc and Mn(TPNMe2-TFPP)OAc. Presumably, not only the axial ligation of imidazole to the four-coordinate Mn(III)-center, but also the steric and electronic influences of aryl-substituents on the porphyrin periphery affect the selectivity of the catalytic oxidation reaction.

  19. Modeling the formation of some polycyclic aromatic hydrocarbons during the roasting of Arabica coffee samples.

    Science.gov (United States)

    Houessou, Justin Koffi; Goujot, Daniel; Heyd, Bertrand; Camel, Valerie

    2008-05-28

    Roasting is a critical process in coffee production, as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot-spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, for roasting conditions ranging from 5 to 20 min. Several PAHs were determined in both roasted coffee samples and green coffee samples. Different models were tested, with more or less assumptions on the chemical phenomena, with a view to predict the system global behavior. Two kinds of models were used and compared: kinetic models (based on Arrhenius law) and statistical models (neural networks). The numbers of parameters to adjust differed for the tested models, varying from three to nine for the kinetic models and from five to 13 for the neural networks. Interesting results are presented, with satisfactory correlations between experimental and predicted concentrations for some PAHs, such as pyrene, benz[a]anthracene, chrysene, and anthracene. PMID:18433138

  20. Oligomer Formation Reactions of Criegee Intermediates in the Ozonolysis of Small Unsaturated Hydrocarbons

    Science.gov (United States)

    Sakamoto, Y.; Inomata, S.; Hirokawa, J.

    2013-12-01

    Secondary organic aerosol (SOA) constitutes a substantial fraction of atmospheric fine particulate matters and has an effect on visibility, climate and human health. One of the major oxidizing processes leading to SOA formation is an ozonolysis of unsaturated hydrocarbons (UHCs).[1] Despite of its importance, the contribution of the ozonolysis of UHCs to the SOA formation in the troposphere is not sufficiently understood due to a lack of information on reaction pathways to produce low volatile compounds. While many studies have previously been focused on SOA formation from the ozonolysis of large UHCs, SOA formation from the ozonolysis of UHCs with less than six carbon atoms have been rarely investigated because their products are expected to be too volatile to contribute to the SOA formation. Very recently, a few studies have reported the SOA formation from the ozonolysis of such small UHCs but chemical mechanisms are still unclear. [2-4] In order to understand SOA formation from the ozonolysis of the small UHCs, this study investigated gas- and particle-phase products in laboratory experiments with a Teflon bag using a negative ion chemical ionization mass spectrometry (NI-CIMS) with chloride ion transfer for chemical ionization. This technique is suitable for analysis of compounds such as carboxylic acids and hydroperoxides expected to be produced in the ozonolysis of UHCs with less fragmentation, high selectivity, and high sensitivity. In the particle-phase analysis, SOAs collected on a PTFE filter were heated, and thermally desorbed compounds were analyzed. In the gas-phase analysis, series of peaks with an interval of a mass-to-charge ratio equal to the molecular weight of a Criegee intermediate formed in their ozonolysis were observed. These peaks were attributed to oligomeric hydroperoxides composed of Criegee intermediates as a chain unit. These oligomeric hydroperoxides were also observed in the particle-phase analysis, indicating that the oligomeric

  1. Forecast of phase state and composition of hydrocarbon systems of subsalt formations of the north Caspian region

    International Nuclear Information System (INIS)

    Full text : Major concentrations of hydrocarbon resources of the Caspian basin are associated with deep horizons. In experimental investigations the forecast of hydrocarbon phase state at the great depths of the oil, gas condensate and gas fields of Precaspian basin has been made and the postion petroleum within the phase-genetic range of the vertical zonation of hydrocarbons from the Precaspain are has been determined from a series of geological and geochemical indices (composition petroleum, individual composition of light and heavy fractions of hydrocarbons. The extended catagenesis zonation and consequently, a low temperature gradient of west and south areas have predetermined generation of gas-condensate and gas pools. Ona can assign those systems to supercritical under saturated systems associated with the high temperature and pressure. The violation of a normal relation in a distribution of liquid and gaseous phases exhibited in those systems is owed to the occurrence of acid components in the composition of formation gas. The content of condensate and gas factor are controlled by the concentration of acid components of formation system. The The higher content of acid components (Hs, S, CO2) in formation gas the lower is the condensate content and gas factor of the oil.

  2. Electrolysis of trichloromethylated organic compounds under aerobic conditions catalyzed by the B12 model complex for ester and amide formation.

    Science.gov (United States)

    Shimakoshi, Hisashi; Luo, Zhongli; Inaba, Takuya; Hisaeda, Yoshio

    2016-06-21

    The electrolysis of benzotrichloride at -0.9 V vs. Ag/AgCl in the presence of the B12 model complex, heptamethyl cobyrinate perchlorate, in ethanol under aerobic conditions using an undivided cell equipped with a platinum mesh cathode and a zinc plate anode produced ethylbenzoate in 56% yield with 92% selectivity. The corresponding esters were obtained when the electrolysis was carried out in various alcohols such as methanol, n-propanol, and i-propanol. Benzoyl chloride was detected by GC-MS during the electrolysis as an intermediate for the ester formation. When the electrolysis was carried out under anaerobic conditions, partially dechlorinated products, 1,1,2,2-tetrachloro-1,2-diphenylethane and 1,2-dichlorostilibenes (E and Z forms), were obtained instead of an ester. ESR spin-trapping experiments using 5,5,-dimethylpyrroline N-oxide (DMPO) revealed that the corresponding oxygen-centered radical and carbon-centered radical were steadily generated during the electrolyses under aerobic and anaerobic conditions, respectively. Applications of the aerobic electrolysis to various organic halides, such as substituted benzotrichlorides, are described. Furthermore, the formation of amides with moderate yields by the aerobic electrolysis of benzotrichloride catalyzed by the B12 model complex in the presence of amines in acetonitrile is reported. PMID:27071703

  3. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products.

    Science.gov (United States)

    Ji, Yuefei; Kong, Deyang; Lu, Junhe; Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo

    2016-08-01

    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 (SO4(-)) with TBBPA was determined to be 5.27×10(10)M(-1)s(-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 SO4(-). 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 6-10h. 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. PMID:27107323

  4. Direct hydrocarbons formation from CH{sub 4} and CO{sub 2} by non-thermal plasma

    Energy Technology Data Exchange (ETDEWEB)

    Pham, M.H.; Tatibouet, J.M.; Batiot-Dupeyrat, C. [Univ. de Poitiers, Poitiers (France). Centre national de la recherche scientifique, Laboratoire de Catalyse en Chimie Organique

    2010-07-01

    Methane (CH{sub 4}) is typically burned to produce heat, the most degraded form of energy. This paper presented a possible way to conserve fossil carbon resources and limit carbon dioxide (CO{sub 2}) emissions by transforming methane into a chemical feedstock. The Fischer-Tropsch process is one of the possible ways of producing hydrocarbons by reforming CH{sub 4} by CO{sub 2} to obtain a mixture of carbon monoxide (CO) and hydrogen (H{sub 2}). However, previous studies have shown that hydrocarbons can by produced directly from a CH{sub 4} and CO{sub 2} mixture by non-thermal plasma, thereby avoiding the Fischer-Tropsch synthesis. This paper presented the results obtained in a coaxial dielectric discharge barrier (DBD) reactor for hydrocarbon formation by varying either the CH{sub 4}/CO{sub 2} ratio or the input energy. The main products were C{sub 2} to C{sub 4} alkanes. The increasing hydrocarbons to CO ratio with the CH{sub 4}/CO{sub 2} initial ratio suggests a radical type mechanism. It was concluded that a 15 percent hydrocarbon yield can be obtained in a single pass with only a short loss of initial carbon. 1 ref.

  5. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.

    Science.gov (United States)

    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M

    2016-07-27

    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  6. Identification of an arylalkylamine N-acyltransferase from Drosophila melanogaster that catalyzes the formation of long-chain N-acylserotonins

    Science.gov (United States)

    Dempsey, Daniel R.; Jeffries, Kristen A.; Anderson, Ryan L.; Carpenter, Anne-Marie; Ospina, Santiago Rodriguez; Merkler, David J.

    2014-01-01

    Arylalkylamine N-acyltransferase-like 22 (AANATL2) from Drosophila melanogaster was expressed and shown to catalyze the formation of long-chain N-acylserotonins and N-acydopamines. Subsequent identification of endogenous amounts of N-acylserotonins and colocalization of these fatty acid amides and AANATL2 transcripts gives supporting evidence that AANATL2 has a role in the biosynthetic formation of these important cell signalling lipids. PMID:24444601

  7. A 4D synchrotron X-ray tomography study of the formation of hydrocarbon migration pathways in heated organic-rich shale

    CERN Document Server

    Panahi, Hamed; Renard, Francois; Mazzini, Adriano; Scheibert, Julien; Dysthe, Dag Kristian; Jamtveit, Bjorn; Malthe-Sørenssen, Anders; Meakin, Paul

    2014-01-01

    Recovery of oil from oil shales and the natural primary migration of hydrocarbons are closely related processes that have received renewed interests in recent years because of the ever tightening supply of conventional hydrocarbons and the growing production of hydrocarbons from low permeability tight rocks. Quantitative models for conversion of kerogen into oil and gas and the timing of hydrocarbon generation have been well documented. However, lack of consensus about the kinetics of hydrocarbon formation in source rocks, expulsion timing and how the resulting hydrocarbons escape from or are retained in the source rocks motivates further investigation. In particular, many mechanisms for the transport of hydrocarbons from the source rocks in which they are generated into adjacent rocks with higher permeabilities and smaller capillary entry pressures have been proposed, and a better understanding of this complex process (primary migration) is needed. To characterize these processes it is imperative to use the ...

  8. Electrochemical reduction of CO2 to formate catalyzed by electroplated tin coating on copper foam

    Science.gov (United States)

    Wang, Yan; Zhou, Jing; Lv, Weixin; Fang, Hailin; Wang, Wei

    2016-01-01

    Sn/f-Cu electrode has been prepared by electrodeposition Sn on a Cu foam substrate in aqueous plating solution, which has been used as the cathode for electrochemical reduction of carbon dioxide (CO2) in aqueous KHCO3 solution. Here, we have explored the effects of the deposition time and the electrolysis potential on the Faradaic efficiency for producing formate. The results demonstrate that maximum Faradaic efficiency of 83.5% is obtained at -1.8 V vs. Ag/AgCl when the Sn/f-Cu electrode is prepared by electrodeposition for 35 min. The Sn/f-Cu electrode exhibits excellent catalytic activity for CO2 reduction compared with the Cu foam electrode and the Sn plate electrode. The average current density and the production rate of formate for the Sn/f-Cu electrode are more than twice those for the Sn plate electrode during electrochemical reduction of CO2.

  9. C–C Bond formation catalyzed by natural gelatin and collagen proteins

    OpenAIRE

    Dennis Kühbeck; Basab Bijayi Dhar; Eva-Maria Schön; Carlos Cativiela; Vicente Gotor-Fernández; David Díaz Díaz

    2013-01-01

    The activity of gelatin and collagen proteins towards C-C bond formation via Henry (nitroaldol) reaction between aldehydes and nitroalkanes is demonstrated for the first time. Among other variables, protein source, physical state and chemical modification influence product yield and kinetics, affording the nitroaldol products in both aqueous and organic media under mild conditions. Significantly, the scale-up of the process between 4-nitrobenzaldehyde and nitromethane is successfully achieved...

  10. Investigation of UVC Induced DNA Damage Formation and Photolyase Catalyzed Repair of Cyclobutane Pyrimidine Dimers

    OpenAIRE

    Kundu, Lal Mohan

    2005-01-01

    Gradual depletion of the ozone layer and consequently, increased ultraviolet (UV) radiation on the Earth's surface induces DNA-lesions inside the genome, thereby causing mutations. Three kinds of photoproducts are mainly formed, namely: cyclobutane pyrimidine dimers (CPD), pyrimidine-(6-4)-pyrimidone dimer [(6-4)PP] and the Dewar valence isomer of (6-4)PP lesion. The formation of these photolesions is a major cause of cell death (aging) and fatal disease like skin cancer. ...

  11. Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Hui [Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084 (China); Energy Research Institute, University of Leeds, Leeds LS2 9JT (United Kingdom); Wu, Chunfei, E-mail: c.wu@leeds.ac.uk [Energy Research Institute, University of Leeds, Leeds LS2 9JT (United Kingdom); Onwudili, Jude A. [Energy Research Institute, University of Leeds, Leeds LS2 9JT (United Kingdom); Meng, Aihong [Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084 (China); Zhang, Yanguo, E-mail: zhangyg@tsinghua.edu.cn [Key Laboratory for Thermal Science and Power Engineering of Ministry of Education, Department of Thermal Engineering, Tsinghua University, Beijing 100084 (China); Williams, Paul T., E-mail: p.t.williams@leeds.ac.uk [Energy Research Institute, University of Leeds, Leeds LS2 9JT (United Kingdom)

    2015-02-15

    Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.

  12. Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

    International Nuclear Information System (INIS)

    Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock

  13. Palynofacies characterization for hydrocarbon source rock evaluation in the Subathu Formation of Marhighat, Sirmaur district, Himachal Pradesh

    Indian Academy of Sciences (India)

    O P Thakur; N N Dogra

    2011-10-01

    This paper deals with the hydrocarbon source rock evaluation of the Subathu Formation exposed at Marhighat on Sarahan–Narag road in Sirmaur district of Himachal Pradesh. Hydrocarbon potential of these sediments is estimated on the basis of palynofacies analysis and thermal alteration index (TAI) values based on the fossil spores/pollen colouration. The analyses are based on the classification and hydrocarbon generation potential of plant derived dispersed organic matter present in the sediments. The palynofacies analysis of Subathu Formation in the area reveal moderate to rich organic matter, with amorphous organic matter constituting the bulk of the total organic matter, followed by charcoal, biodegraded organic matter, fungal remains, spores/pollen and structured terrestrial organic matter. The TAI value for the organic matter in these sediments has been ascertained as 3.00. A dominance of the sapropelic facies (amorphous organic matter) and the measured TAI values for the Subathu sediments in the Marhighat area suggests a good source-rock potential for the hydrocarbon generation.

  14. Release behavior and formation mechanism of polycyclic aromatic hydrocarbons during coal pyrolysis.

    Science.gov (United States)

    Gao, Meiqi; Wang, Yulong; Dong, Jie; Li, Fan; Xie, Kechang

    2016-09-01

    Polycyclic aromatic hydrocarbons (PAHs) are major environmental pollutants. They have attracted considerable attention due to their severe potential carcinogenic, mutagenic and genotoxic effects on human health. In this study, five different rank coals from China were pyrolyzed using pyro-probe CDS 5250 and the release behavior of 16 PAHs under different pyrolysis conditions were studied by Gas Chromatography-Mass Spectrometer (GC-MS). The structural characteristics of the five coals were determined by Cross-Polarization/Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) spectroscopy, and then the factors influencing the formation of PAHs during coal pyrolysis were discussed together with the coal structural data. It was shown that the amount of PAHs generated during coal pyrolysis was largely related to coal rank and followed the order of medium metamorphic coal > low metamorphic coal > high metamorphic coal. The amount of total PAHs varied as the temperature was increased from 400 °C to 1200 °C, which showed a trend of first increasing and then decreasing, with the maximum value at 800 °C. Moreover, the species of PAHs released varied with pyrolysis temperatures. When the temperature was lower than 800 °C, the small ring PAHs were the most abundant, while the proportion of heavy rings increased at higher temperature. The results indicate that the formation of PAHs during coal pyrolysis depends on the structure of the coal. The species and amounts of PAHs generated during coal pyrolysis are closely related to the contents of protonated aromatic carbons and bridging ring junction aromatic carbons present in the coal structure. PMID:27239965

  15. Interface formation between hydrocarbon ring molecules and III-V semiconductor surfaces

    International Nuclear Information System (INIS)

    In this work a systematical study to investigate the adsorption structures of small hydrocarbon ring shaped molecules on III-V semiconductor surfaces with Photo-Emission Spectroscopy (PES), Reflectance Anisotropy Spectroscopy (RAS), Scanning Tunneling Microscopy (STM) as well as Low Electron Energy Diffraction (LEED) was performed. To investigate the influence of the surface structure in detail the surface dimer configuration to the adsorption process of organic molecules GaAs(001) surfaces, the c(4 x 4), the (2 x 4) and the (4 x 2) have been investigated as well as the adsorption of cyclopentene on the InP(001)(2 x 4) reconstructed surface. In the direct comparison it is shown that cyclopentene bonds to the InP(001)(2 x 4) surface via a cycloaddition like reaction. During this adsorption the double bond splits which is in contrast to the adsorption of cyclopentene on the GaAs(001) surfaces. Therefrom it is concluded that the surface geometry has an influence on the resulting adsorption structure. In order to investigate the influence of the intra-molecular double bonds, cyclopentene (one double bond), 1,4-cyclohexadiene (two double bonds) and benzene (three double bonds) were used for the characterization of the interface formation. With the investigations on the GaAs(001) reconstructed surfaces it was shown that a dependency of the bonding configuration on the intra-molecular double bonds exists. During the adsorption of cyclopentene no evidence was found that the double bond has to be involved in the interface formation while during the adsorption of 1,4-cyclohexadiene and benzene the double bonds are involved. Furthermore it was found that a bonding to As atoms of the surface is more likely than a bonding to Ga atoms. (orig.)

  16. Interface formation between hydrocarbon ring molecules and III-V semiconductor surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Passmann, Regina

    2008-08-15

    In this work a systematical study to investigate the adsorption structures of small hydrocarbon ring shaped molecules on III-V semiconductor surfaces with Photo-Emission Spectroscopy (PES), Reflectance Anisotropy Spectroscopy (RAS), Scanning Tunneling Microscopy (STM) as well as Low Electron Energy Diffraction (LEED) was performed. To investigate the influence of the surface structure in detail the surface dimer configuration to the adsorption process of organic molecules GaAs(001) surfaces, the c(4 x 4), the (2 x 4) and the (4 x 2) have been investigated as well as the adsorption of cyclopentene on the InP(001)(2 x 4) reconstructed surface. In the direct comparison it is shown that cyclopentene bonds to the InP(001)(2 x 4) surface via a cycloaddition like reaction. During this adsorption the double bond splits which is in contrast to the adsorption of cyclopentene on the GaAs(001) surfaces. Therefrom it is concluded that the surface geometry has an influence on the resulting adsorption structure. In order to investigate the influence of the intra-molecular double bonds, cyclopentene (one double bond), 1,4-cyclohexadiene (two double bonds) and benzene (three double bonds) were used for the characterization of the interface formation. With the investigations on the GaAs(001) reconstructed surfaces it was shown that a dependency of the bonding configuration on the intra-molecular double bonds exists. During the adsorption of cyclopentene no evidence was found that the double bond has to be involved in the interface formation while during the adsorption of 1,4-cyclohexadiene and benzene the double bonds are involved. Furthermore it was found that a bonding to As atoms of the surface is more likely than a bonding to Ga atoms. (orig.)

  17. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

    Science.gov (United States)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Kacarab, Mary; Cocker, David R

    2016-06-21

    Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition. PMID:27177154

  18. Methanol formation from CO2 catalyzed by Fe3S4{111}: formate versus hydrocarboxyl pathways.

    Science.gov (United States)

    Roldan, A; de Leeuw, N H

    2016-07-01

    Carbon capture and utilisation is one of the most promising techniques to minimize the impact of the increasing amount of carbon dioxide in the atmosphere. Recently, the mineral greigite was shown to be capable of catalysing CO2 conversion, leading to useful small organic molecules. Here, we have carried out a systematic study of the adsorption and selective reduction of CO2 on the Fe3S4{111} surface. We have considered both formate and hydrocarboxyl key intermediates, leading to different reaction pathways via Eley-Rideal and Langmuir-Hinshelwood mechanisms, and we have built a kinetic model considering the wide range of intermediates in the reaction network. Our results show that the mechanism to produce formic acid takes place via formate intermediate mostly on FeA sites, while methanol is formed via hydrocarboxyl intermediates on FeB sites. From the kinetic model, we have derived a reaction constant comparison and determined the limiting step rates. The overall process takes place under very mild conditions, requiring only a small energy input that might come from a chemiosmotic potential. PMID:27108755

  19. Kinetics of Methanol Carbonylation to Methyl Formate Catalyzed by Sodium Methoxide

    Institute of Scientific and Technical Information of China (English)

    Liang Chen; Jianghong Zhang; Ping Ning; Yunhua Chen; Wenbing Wu

    2004-01-01

    Kinetics of synthesis of methyl formate from carbon monoxide and methanol, using sodium methoxide as the catalyst and pyridine as the promoter in a batch reactor, was studied. Kinetic parameters such as the apparent reaction orders, the rate constant and the apparent activation energies were obtained.The experimental results showed that both the reaction orders with respect to CO and methanol equal to 1, the general reaction kinetic equation is (-r)=-dp(CO)/dt=k. p(CO).[MeOH], and the rate constant is decreased 6.44 k J/mol and the rate constant had increased more than 1.5 times when pyridine was used as the promoter in the catalyst system.

  20. Reservoir petrophysics and hydrocarbon occurrences of the Bahariya Formation, Alamein-Yidma fields, Western Desert of Egypt

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Aziz Younes, Mohamed [Alexandria Univ. (Egypt). Geology Dept.

    2012-12-15

    The Bahariya Formation of Cenomanian age is considered to be one of the main oil and gas accumulations in most of the fields of the Western Desert basins. The lithostratigraphic succession of the Bahariya Formation is classified into two main sand units (Unit I and Unit III) separated by shalesiltstone (Unit II). The sandstone of unit-I and III is characterized by being highly enriched in shale content especially glauconite in all wells of the Alamein Field, that has an obvious negative effect on the porosity and oil saturation, where the glauconite increases the grain density of sandstone reservoirs from 2.65 g/cm{sup 3} up to 2.71 g/cm{sup 3}. The well logging data and petrophysical characteristics conducted on Alamein well-28 involving analysis of 30 core samples, were used to evaluate the reservoir characterization and hydrocarbon potentialities. The petrophysical parameters indicate that the primary porosity values are between 8.7 and 29.1%. Decreasing porosity is related to the increase of shale content from 9 to 13%, which occurs as a dispersed habitat. The water saturation changes from 43 to 80%, while the hydrocarbon saturation ranges from 12.1 to 37%. Promising hydrocarbon accumulations are displayed by the sandstone of unit-III due to increased hydrocarbon saturation and effective porosity, thus reflecting the high quality reservoir of this unit. The irreducible and movable hydrocarbon distribution shows a general increase at the eastern and western flanks of the faulted anticline in the Alamein-Yidma fields. The biomarker characteristics and stable carbonisotopic composition of the Bahariya crude oils recovered from the Alamein Field show no obvious variations among them. These oils are paraffinic, containing little branched or cyclic materials waxy n-alkanes(C{sub 25}-C{sub 31}) and characterized by high API gravity, low sulfur content, oleanane index < 2% and moderately high pristane/phytaneratio > 1 and CPI > 1 and the canonical variable parameter is

  1. Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

    Science.gov (United States)

    Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

    2016-07-01

    Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. PMID:27131033

  2. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    Science.gov (United States)

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  3. The methanol-to-hydrocarbons reaction : Influence of acid strength on the mechanism of olefin formation

    OpenAIRE

    2010-01-01

    The methanol-to-hydrocarbons (MTH) reaction is a flexible alternative step in the upgrading of natural gas, coal or biomass. By tuning the catalyst and process conditions, methanol can be converted into a variety of hydrocarbon products including gasoline and polymer-grade olefins. While the reaction has been known for many years, reaction mechanisms are still not fully understood. Most previous mechanistic studies have been performed on aluminosilicate zeolites, so the aim of the present wor...

  4. Maximum Topological Distances Based Indices as Molecular Descriptors for QSPR. 4. Modeling the Enthalpy of Formation of Hydrocarbons from Elements

    Directory of Open Access Journals (Sweden)

    Andrey A. Toropov

    2001-06-01

    Full Text Available The enthalpy of formation of a set of 60 hydroarbons is calculated on the basis of topological descriptors defined from the distance and detour matrices within the realm of the QSAR/QSPR theory. Linear and non-linear polynomials fittings are made and results show the need to resort to higher-order regression equations in order to get better concordances between theoretical results and experimental available data. Besides, topological indices computed from maximum order distances seems to yield rather satisfactory predictions of heats of formation for hydrocarbons.

  5. 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.

  6. Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

    OpenAIRE

    Gadi Ranjith Kumar; Yalla Kiran Kumar; Ruchir Kant; Maddi Sridhar Reddy

    2014-01-01

    The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions.

  7. Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

    OpenAIRE

    Kumar, Gadi Ranjith; Kumar, Yalla Kiran; Kant, Ruchir; Reddy, Maddi Sridhar

    2014-01-01

    The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions.

  8. Palladium-Catalyzed Carbonylation of (Hetero)Aryl, Alkenyl and Allyl Halides by Means of N-Hydroxysuccinimidyl Formate as CO Surrogate.

    Science.gov (United States)

    Barré, Anaïs; Ţînţaş, Mihaela-Liliana; Alix, Florent; Gembus, Vincent; Papamicaël, Cyril; Levacher, Vincent

    2015-07-01

    An efficient Pd-catalyzed carbonylation protocol is described for the coupling of a large panel of aryl, heteroaryl, benzyl, vinyl and allyl halides 2 with the unusual N-hydroxysuccinimidyl (NHS) formate 1 as a CO surrogate to afford the corresponding valuable NHS esters 3. High conversion to the coupling products was achieved with up to 98% yield by means of Pd(OAc)2/Xantphos catalyst system. PMID:26098725

  9. Nile Red Detection of Bacterial Hydrocarbons and Ketones in a High-Throughput Format

    Energy Technology Data Exchange (ETDEWEB)

    Pinzon, NM; Aukema, KG; Gralnick, JA; Wackett, LP

    2011-06-28

    A method for use in high-throughput screening of bacteria for the production of long-chain hydrocarbons and ketones by monitoring fluorescent light emission in the presence of Nile red is described. Nile red has previously been used to screen for polyhydroxybutyrate (PHB) and fatty acid esters, but this is the first report of screening for recombinant bacteria making hydrocarbons or ketones. The microtiter plate assay was evaluated using wild-type and recombinant strains of Shewanella oneidensis and Escherichia coli expressing the enzyme OleA, previously shown to initiate hydrocarbon biosynthesis. The strains expressing exogenous Stenotrophomonas maltophilia oleA, with increased levels of ketone production as determined by gas chromatography-mass spectrometry, were distinguished with Nile red fluorescence. Confocal microscopy images of S. oneidensis oleA-expressing strains stained with Nile red were consistent with a membrane localization of the ketones. This differed from Nile red staining of bacterial PHB or algal lipid droplets that showed intracellular inclusion bodies. These results demonstrated the applicability of Nile red in a high-throughput technique for the detection of bacterial hydrocarbons and ketones. IMPORTANCE In recent years, there has been renewed interest in advanced biofuel sources such as bacterial hydrocarbon production. Previous studies used solvent extraction of bacterial cultures followed by gas chromatography-mass spectrometry (GC-MS) to detect and quantify ketones and hydrocarbons (Beller HR, Goh EB, Keasling JD, Appl. Environ. Microbiol. 76: 1212-1223, 2010; Sukovich DJ, Seffernick JL, Richman JE, Gralnick JA, Wackett LP, Appl. Environ. Microbiol. 76: 3850-3862, 2010). While these analyses are powerful and accurate, their labor-intensive nature makes them intractable to high-throughput screening; therefore, methods for rapid identification of bacterial strains that are overproducing hydrocarbons are needed. The use of high

  10. Evidence for the formation of an enamine species during aldol and Michael-type addition reactions promiscuously catalyzed by 4-oxalocrotonate tautomerase.

    Science.gov (United States)

    Poddar, Harshwardhan; Rahimi, Mehran; Geertsema, Edzard M; Thunnissen, Andy-Mark W H; Poelarends, Gerrit J

    2015-03-23

    The enzyme 4-oxalocrotonate tautomerase (4-OT), which has a catalytic N-terminal proline residue (Pro1), can promiscuously catalyze various carbon-carbon bond-forming reactions, including aldol condensation of acetaldehyde with benzaldehyde to yield cinnamaldehyde, and Michael-type addition of acetaldehyde to a wide variety of nitroalkenes to yield valuable γ-nitroaldehydes. To gain insight into how 4-OT catalyzes these unnatural reactions, we carried out exchange studies in D2 O, and X-ray crystallography studies. The former established that H-D exchange within acetaldehyde is catalyzed by 4-OT and that the Pro1 residue is crucial for this activity. The latter showed that Pro1 of 4-OT had reacted with acetaldehyde to give an enamine species. These results provide evidence of the mechanism of the 4-OT-catalyzed aldol and Michael-type addition reactions in which acetaldehyde is activated for nucleophilic addition by Pro1-dependent formation of an enamine intermediate. PMID:25728471

  11. Experimental investigation of hydrocarbon formation and transformation under Earth´s upper mantle conditions

    OpenAIRE

    Kolesnikov, Anton

    2010-01-01

    The theory of the abyssal abiotic petroleum origin considers oil and natural gas to begenerated in the Earth’s upper mantle. Hydrocarbons migrate further through the deep faults into the Earth’s crust, where they can form oil and gas deposits in any kind of rock in any kind of structural position. Until recently one of the main obstacles for further development of this theory has been the lack of the data covering processes of generation and transformations of hydrocarbons. Experimental data,...

  12. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-01

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling. PMID:27439145

  13. Polycyclic aromatic hydrocarbons and dust in regions of massive star formation

    NARCIS (Netherlands)

    Peeters, Els

    2002-01-01

    Polycyclic Aromatic Hydrocarbons (PAHs) are known on earth as a large family of tarry materials naturally present in for example coal and crude oil. In addition, they are also formed in the combustion of all sorts of carbonaceous fuels and hence are found in auto exhaust, cigarette smoke, candle soo

  14. Hydrocarbons in the Hauptsalz formation of the Gorleben salt dome. Content, distribution and origin

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, Maximilian; Hammer, Joerg; Ostertag-Henning, Christian [Federal Institute for Geosciences and Natural Resources (BGR), Hannover (Germany)

    2015-07-01

    In the frame of the geological exploration of the Gorleben salt dome (November 2010 to November 2012) concentrations and compositions of hydrocarbons occuring in the main rock salt (Hauptsalz, Stassfurt series, z2) have been investigated. These exploration works followed former investigations of Gerling et al. (2002) and Bornemann et al. (2008). In order to get fresh, unaltered and representative samples beyond the EDZ (excavation damaged zone) for mineralogical and geochemical analyses, about 45 boreholes have been drilled at the 840 m level of the Gorleben exploration mine. These boreholes have been arranged in equal distances (depending on the mine structure) alongside crosscut 1 west (each 6 m long) and crosscut 1 east (each 9 m long). In addition 20 packer boreholes (10 packer boreholes per crosscut) for pressure build-up recording and hydrocarbon sampling have also been established. Immediately after drilling, core samples from the Hauptsalz for organic geochemical analyses have been retrieved and were dissolved in deionised and degased water. The results of analyses of about 210 samples scattered over all 45 boreholes reveal a total background concentration of hydrocarbons (C{sub 1} to C{sub 40}) of 0,24 mg/kg. 70 samples have concentrations between 1 mg/kg and 50 mg/kg (average 2,66 mg/kg) with 5 outliers up to 442 mg/kg in crosscut 1 west (Hammer et al. 2012, 2013). The drill cores have been investigated and documented by using ultraviolet light (l = 254 nm) in respect of visible indications of the existence of fluorescing aromatic hydrocarbons. Analyses revealed a high level of heterogeneous hydrocarbon distribution in the shape of isolated, irregular streaks, clusters, clouds and occasionally layers mainly located in recrystallized zones of the Hauptsalz. Thin sections and thick sections showed that hydrocarbons in z2HS1 (Knaeuelsalz) and z2HS2 (Streifensalz) samples are either located as black to brownish dendritical fluid inclusions alongside the grain

  15. Low Temperature Formation of Nitrogen-substituted Polycyclic Aromatic Hydrocarbons (PANHs)- Barrierless Routes to Dihydro(iso)quinolines

    Science.gov (United States)

    Parker, Dorian S. N.; Yang, Tao; Dangi, Beni B.; Kaiser, Ralf. I.; Bera, Partha P.; Lee, Timothy J.

    2015-12-01

    Meteorites contain bio-relevant molecules such as vitamins and nucleobases, which consist of aromatic structures with embedded nitrogen atoms. Questions remain over the chemical mechanisms responsible for the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) in extraterrestrial environments. By exploiting single collision conditions, we show that a radical mediated bimolecular collision between pyridyl radicals and 1,3-butadiene in the gas phase forms nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) 1,4-dihydroquinoline and to a minor amount 1,4-dihydroisoquinoline. The reaction proceeds through the formation of a van der Waals complex, which circumnavigates the entrance barrier implying it can operate at very low kinetic energy and therefore at low temperatures of 10 K as present in cold molecular clouds such as TMC-1. The discovery of facile de facto barrierless exoergic reaction mechanisms leading to PANH formation could play an important role in providing a population of aromatic structures upon which further photo-processing of ice condensates could occur to form nucleobases.

  16. Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

    Science.gov (United States)

    Rollins, Harry W.; Petkovic, Lucia M.; Ginosar, Daniel M.

    2011-02-01

    Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

  17. Formation and Accumulation of Hydrocarbons in the Central Uplift, Dongying Depression

    Institute of Scientific and Technical Information of China (English)

    Li Sumei; Qiu Guiqiang; Gao Yongjin; Jiang Zhenxue

    2006-01-01

    A large number of crude oil and rock samples from various oil pools of the Central Uplift in Dongying Depression were investigated to reveal the origin and accumulation of hydrocarbons. The results showed that the composition and areal distribution of hydrocarbons vary with the location of the oil pools. An increasing trend of gammacerane/C30-hopane and steranes/hopanes but a decreasing trend of prystane/phytane (Pr/Ph) and 18(H)-/17(H)-trisnorhopane (Ts/Tm) ratios were observed from southwest to northeast. This indicates a variation of source rocks and hydrocarbon properties. An increasing trend of water salinity with much more input of algae-rich microorganisms in the deposition environment of the source rock was observed from southwest to northeast. However, the thermal maturity of the source rocks showed a decreasing trend in the same direction. Oil-to-oil and oil-to-source rock correlations showed that most oils were sourced from Es3 and Es4 members with a burial depth of more than 3,000-3,150 m and 2,700 m respectively. The oils in the Shinan and Ying 11 sand bodies, which were generally mixed with the Es4 sourced oils, came mostly from Es3 mudstones. It is quite significant that the Es4 derived oils migrated vertically for hundreds of meters and accumulated in an overlying lithologic pool of the Es3m, i.e., Ying 11 synclinal lithologic pool, which suggests that the mechanisms of migration and accumulation for subtle oil pools in the Dongying Depression are more complex than that of the previously expected.

  18. Estimation of subsurface formation temperature in the Tarim Basin, northwest China: implications for hydrocarbon generation and preservation

    Science.gov (United States)

    Liu, Shaowen; Lei, Xiao; Feng, Changge; Hao, Chunyan

    2016-07-01

    Subsurface formation temperature in the Tarim Basin, northwest China, is vital for assessment of hydrocarbon generation and preservation, and of geothermal energy potential. However, it has not previously been well understood, due to poor data coverage and a lack of highly accurate temperature data. Here, we combined recently acquired steady-state temperature logging data with drill stem test temperature data and measured rock thermal properties, to investigate the geothermal regime and estimate the subsurface formation temperature at depth in the range of 1000-5000 m, together with temperatures at the lower boundary of each of four major Lower Paleozoic marine source rocks buried in this basin. Results show that heat flow of the Tarim Basin ranges between 26.2 and 66.1 mW/m2, with a mean of 42.5 ± 7.6 mW/m2; the geothermal gradient at depth of 3000 m varies from 14.9 to 30.2 °C/km, with a mean of 20.7 ± 2.9 °C/km. Formation temperature estimated at the depth of 1000 m is between 29 and 41 °C, with a mean of 35 °C, while 63-100 °C is for the temperature at the depth of 3000 m with a mean of 82 °C. Temperature at 5000 m ranges from 97 to 160 °C, with a mean of 129 °C. Generally spatial patterns of the subsurface formation temperature at depth are basically similar, characterized by higher temperatures in the uplift areas and lower temperatures in the sags, which indicates the influence of basement structure and lateral variations in thermal properties on the geotemperature field. Using temperature to identify the oil window in the source rocks, most of the uplifted areas in the basin are under favorable condition for oil generation and/or preservation, whereas the sags with thick sediments are favorable for gas generation and/or preservation. We conclude that relatively low present-day geothermal regime and large burial depth of the source rocks in the Tarim Basin are favorable for hydrocarbon generation and preservation. In addition, it is found that the

  19. Estimation of subsurface formation temperature in the Tarim Basin, northwest China: implications for hydrocarbon generation and preservation

    Science.gov (United States)

    Liu, Shaowen; Lei, Xiao; Feng, Changge; Hao, Chunyan

    2015-10-01

    Subsurface formation temperature in the Tarim Basin, northwest China, is vital for assessment of hydrocarbon generation and preservation, and of geothermal energy potential. However, it has not previously been well understood, due to poor data coverage and a lack of highly accurate temperature data. Here, we combined recently acquired steady-state temperature logging data with drill stem test temperature data and measured rock thermal properties, to investigate the geothermal regime and estimate the subsurface formation temperature at depth in the range of 1000-5000 m, together with temperatures at the lower boundary of each of four major Lower Paleozoic marine source rocks buried in this basin. Results show that heat flow of the Tarim Basin ranges between 26.2 and 66.1 mW/m2, with a mean of 42.5 ± 7.6 mW/m2; the geothermal gradient at depth of 3000 m varies from 14.9 to 30.2 °C/km, with a mean of 20.7 ± 2.9 °C/km. Formation temperature estimated at the depth of 1000 m is between 29 and 41 °C, with a mean of 35 °C, while 63-100 °C is for the temperature at the depth of 3000 m with a mean of 82 °C. Temperature at 5000 m ranges from 97 to 160 °C, with a mean of 129 °C. Generally spatial patterns of the subsurface formation temperature at depth are basically similar, characterized by higher temperatures in the uplift areas and lower temperatures in the sags, which indicates the influence of basement structure and lateral variations in thermal properties on the geotemperature field. Using temperature to identify the oil window in the source rocks, most of the uplifted areas in the basin are under favorable condition for oil generation and/or preservation, whereas the sags with thick sediments are favorable for gas generation and/or preservation. We conclude that relatively low present-day geothermal regime and large burial depth of the source rocks in the Tarim Basin are favorable for hydrocarbon generation and preservation. In addition, it is found that the

  20. Oxygen exchange reactions catalyzed by vacuolar H(+)-translocating pyrophosphatase. Evidence for reversible formation of enzyme-bound pyrophosphate.

    Science.gov (United States)

    Baykov, A A; Kasho, V N; Bakuleva, N P; Rea, P A

    1994-08-22

    Vacuolar membrane-derived vesicles isolated from Vigna radiata catalyze oxygen exchange between medium phosphate and water. On the basis of the inhibitor sensitivity and cation requirements of the exchange activity, it is almost exclusively attributable to the vacuolar H(+)-pyrophosphatase (V-PPase). The invariance of the partition coefficient and the results of kinetic modeling indicate that exchange proceeds via a single reaction pathway and results from the reversal of enzyme-bound pyrophosphate synthesis. Comparison of the exchange reactions catalyzed by V-PPase and soluble PPases suggests that the two classes of enzyme mediate P(i)-HOH exchange by the same mechanism and that the intrinsic reversibility of the V-PPase is no greater than that of soluble PPases. PMID:8070586

  1. Paraselectivity and Formation of Aromatic Hydrocarbons over ZSM-5 Type Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Unneberg, E.

    1996-12-31

    The zeolite ZSM-5, patented by Mobil Oil Corporation in 1972, is able to convert methanol to gasoline (MTG) and water. Due to the size of the channels, undesired hydrocarbons larger than C{sub 11} are not present in the mixture, and a high octane gasoline is obtained. This has aroused a great deal of interest in the ZSM-5. Rather than being concerned with energy considerations, this doctoral thesis describes syntheses of ZSM-5 and discusses the ZSM-5 as such and studies the possible paraselectivities in various reactions over the catalyst ZSM-5. 774 refs., 113 figs., 54 tabs.

  2. Mechanistic studies related to the metal catalyzed reduction of carbon monoxide to hydrocarbons. Final report, April 1, 1977-June 30, 1985

    International Nuclear Information System (INIS)

    Studies of compounds related to proposed intermediates in the hydrogenation of carbon monoxide over homogeneous and heterogeneous catalysts have been carried out. The synthesis, structure, and reactions of metal formyl compounds have been investigated. The synthesis and desproportionation reactions of hydroxymethyl metal compounds have been explored. Reactions involving interconversion of n5- and n'-C5H5 organometallic compounds have been discovered. New synthetic routes to bimetallic compounds with bridging hydrocarbon ligands have been developed. The first bimetallic compound with a budging CH ligand has been prepared. The hydrocarbation reaction in which the CH bond of a bridging methylidyne complex adds across a carbon-carbon double bond has been discovered. New heterobimetallic compounds linked by a heterodifunctional ligand and heterobimetallic compounds with directly bonded early and late transition metals have been synthesized in a search for new CO hydrogenation catalysts. 36 refs

  3. Formation of Polycyclic Aromatic Hydrocarbons and Nitrogen Containing Polycyclic Aromatic Compounds in Titan's Atmosphere, the Interstellar Medium and Combustion

    Science.gov (United States)

    Landera, Alexander

    2013-12-01

    Several different mechanisms leading to the formation of (substituted) naphthalene and azanaphthalenes were examined using theoretical quantum chemical calculations. As a result, a series of novel synthetic routes to Polycyclic Aromatic Hydrocarbons (PAHs) and Nitrogen Containing Polycyclic Aromatic Compounds (N-PACs) have been proposed. On Earth, these aromatic compounds originate from incomplete combustion and are released into our environment, where they are known to be major pollutants, often with carcinogenic properties. In the atmosphere of a Saturn's moon Titan, these PAH and N-PACs are believed to play a critical role in organic haze formation, as well as acting as chemical precursors to biologically relevant molecules. The theoretical calculations were performed by employing the ab initio G3(MP2,CC)/B3LYP/6-311G** method to effectively probe the Potential Energy Surfaces (PES) relevant to the PAH and N-PAC formation. Following the construction of the PES, Rice-Ramsperger-Kassel-Markus (RRKM) theory was used to evaluate all unimolecular rate constants as a function of collision energy under single-collision conditions. Branching ratios were then evaluated by solving phenomenological rate expressions for the various product concentrations. The most viable pathways to PAH and N-PAC formation were found to be those where the initial attack by the ethynyl (C2H) or cyano (CN) radical toward a unsaturated hydrocarbon molecule led to the formation of an intermediate which could not effectively lose a hydrogen atom. It is not until ring cyclization has occurred, that hydrogen elimination leads to a closed shell product. By quenching the possibility of the initial hydrogen atom elimination, one of the most competitive processes preventing the PAH or N-PAC formation was avoided, and the PAH or N-PAC formation was allowed to proceed. It is concluded that these considerations should be taken into account when attempting to explore any other potential routes towards

  4. Low-maturity Kulthieth Formation coal : a possible source of polycyclic aromatic hydrocarbons in benthic sediment of the Northern Gulf of Alaska

    International Nuclear Information System (INIS)

    This study addressed the issue of sources of hydrocarbons for benthic sediments in the Gulf of Alaska (GOA) with particular reference to the application of forensic geology to identify end members and to explain the geologic setting and processes affecting the system. Native coals and natural seep oils have been questioned in the past decade as possible sources of background hydrocarbons because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Native coal has also been dismissed as a pollution source because ratios of labile hydrocarbons to total organic carbon for Bering River coal field (BRCF) sources are too low to be consistent with GOA sediments. The authors present evidence that perhaps native coal has been prematurely dismissed as a pollution source because BRCF coals do not represent adequately the geochemical signatures of coals elsewhere in the Kulthieth Formation which have much higher PAH:TOC ratios. The patterns of labile hydrocarbons in these low thermal maturity coals indicate a genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analysis of the coal suggests it is a significant source of PAH, and it was cautioned that source models that do not include this source will underestimate the contribution of native coals to the background hydrocarbon signature in the Gulf of Alaska. 32 refs., 2 tabs., 8 figs

  5. Formation of Combustible Hydrocarbons and H2 during Photocatalytic Decomposition of Various Organic Compounds under Aerated and Deaerated Conditions

    Directory of Open Access Journals (Sweden)

    Sylwia Mozia

    2014-11-01

    Full Text Available A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of “green energy” production.

  6. Formation of hydrocarbons from acid-Clay suspensions by gamma irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Cruz-Castaneda, J.; Negron-Mendoza, A.; Ramos-Bernal, S. [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, UNAM. Cd. Universitaria, A. P. 70-543, 04510 Mexico (Mexico)

    2013-07-03

    The adsorption of certain organic compounds by clays gives rise to the transformation of the adsorbate through the action of the clays. This phenomenon can be enhanced using ionizing radiation. In this context, these kinds of reactions play an important role in many natural and industrial processes. For example, in oil and gas exploration, the source and trap of petroleum hydrocarbons is frequently clay-rich rocks. Clay-water-based muds are also seen as environmentally friendly alternatives to toxic oil-based fluids. The principal processes that occur in sediments are usually held to be of bacterial action and thermal transformation, which may include thermally induced catalytic alteration of the organic debris. On the other hand, radioactive materials are widely distributed throughout Earth. They were more abundant in the past, but are present in petroleum reservoirs. Their presence induced radioactive bombardment, which may have altered these sediments. This important subject has not been extensively studied. The aim of this work is to study the behavior of fatty acids-like behenic acid-and dicarboxylic acids-like fumaric acid-as model compounds, which are adsorbed in a clay mineral (Na-montmorillonite) and exposed to gamma radiation. The results show that the radiation-induced decomposition of the clay-acid system goes along a definitive path (oxidation), rather than following several modes of simultaneous decomposition, as happens in radiolysis without clay or by heating the system. The main radiolytic products for fatty acids are their corresponding hydrocarbons, with one C-atom less than the original acid.

  7. Mineralogy and geochemistry of alteration induced by hydrocarbon seepage in an evaporite formation; a case study from the Zagros Fold Belt, SW Iran

    International Nuclear Information System (INIS)

    Highlights: • Geochemistry of alterations induced by hydrocarbon seepage are investigated. • Occurrence of jarosite, natroalunite, and sulfur were measured using XRD analysis. • Simultaneous decrease of sulfate and increase of carbonate were detected. • Carbon isotope analysis supports a partial contribution of hydrocarbon in carbonates. • Increase of Cr, Co, Ni, V, Cd, U, Cu, and Zn are detected in altered areas. - Abstract: Leaking hydrocarbon and associated fluids produce a reduced environment which initiates diagenetic reactions in the rocks and soils overlying hydrocarbon reservoirs. This article introduces mineralogical and geochemical alterations induced by hydrocarbon seepages in the Gachsaran evaporite Formation, Masjed Soleiman, Zagros Folded Belt, SW Iran, using various geochemical methods. X-ray diffraction (XRD) analysis revealed two dominant groups of mineralogical changes in the anomalous zone including: (1) spotty occurrences of jarosite, natroalunite, and sulfur; (2) simultaneous decrease of sulfate and increase of carbonate. The δ13C values of carbonate phases vary between −8.9‰ and −32.3‰ which support a partial contribution of hydrocarbon in these phases. pH measurements of rock samples indicated that hydrocarbon seepage causes decrease of pH, though not very significantly. However, pH in areas that show ongoing sour hydrocarbon seepage among rarely pure gypsum beds decrease to −0.09 which produces acid sulfate soil. Trace element concentrations indicated that Cr, Co, Ni, V, Cd, U, Cu, and Zn increase in various patterns around the hydrocarbon seepages excepting the areas with very low pH

  8. A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins.

    Science.gov (United States)

    Dee, Sean J; Bell, Alexis T

    2011-08-22

    An investigation was carried out into the hydrolysis of cellulose dissolved in 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]) and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) catalyzed by mineral acids. Glucose, cellobiose, and 5-hydroxymethylfurfural (5-HMF) were observed as the primary reaction products. The initial rate of glucose formation was determined to be of first order in the concentrations of dissolved glucan and protons and of zero order in the concentration of water. The absence of a dependence on water concentration suggests that cleavage of the β-1,4-glycosidic linkages near chain ends is irreversible. The apparent activation energy for glucose formation is 96 kJ mol(-1). The absence of oligosaccharides longer than cellobiose suggests that cleavage of interior glycosidic bonds is reversible due to the slow diffusional separation of cleaved chains in the highly viscous glucan/ionic liquid solution. Progressive addition of water during the course of glucan hydrolysis inhibited the rate of glucose dehydration to 5-HMF and the formation of humins. The inhibition of glucose dehydration is attributed to stronger interaction of protons with water than the 2-OH atom of the pyranose ring of glucose, the critical step in the proposed mechanism for the formation of 5-HMF. The reduction in humin formation associated with water addition is ascribed to the lowered concentration of 5-HMF, since the formation of humins is suggested to proceed through the condensation polymerization of 5-HMF with glucose. PMID:21809450

  9. The Formation of Pyrroline and Tetrahydropyridine Rings in Amino Acids Catalyzed by Pyrrolysine Synthase (PylD)

    KAUST Repository

    Quitterer, Felix

    2014-06-10

    The dehydrogenase PylD catalyzes the ultimate step of the pyrrolysine pathway by converting the isopeptide L-lysine-Nε-3R-methyl-D-ornithine to the 22nd proteinogenic amino acid. In this study, we demonstrate how PylD can be harnessed to oxidize various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings as constituents of pyrrolysine analogues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric C—C bond formation

    OpenAIRE

    Negishi, Ei-ichi; Tan, Ze; Liang, Bo; Novak, Tibor

    2004-01-01

    An efficient and general method for the synthesis of reduced polypropionates has been developed through the application of asymmetric carboalumination of alkenes catalyzed by dichlorobis(1-neomenthylindenyl)zirconium [(NMI)2ZrCl2]. In this investigation, attention has been focused on those reduced polypropionates that are α-monoheterofunctional and either ω-ethyl or ω-n-propyl. The reaction of 3-buten-1-ol with triethylaluminum (Et3Al) or tripropylaluminum (nPr3Al) in the presence of (NMI)2Zr...

  11. An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric C—C bond formation

    Science.gov (United States)

    Negishi, Ei-ichi; Tan, Ze; Liang, Bo; Novak, Tibor

    2004-01-01

    An efficient and general method for the synthesis of reduced polypropionates has been developed through the application of asymmetric carboalumination of alkenes catalyzed by dichlorobis(1-neomenthylindenyl)zirconium [(NMI)2ZrCl2]. In this investigation, attention has been focused on those reduced polypropionates that are α-monoheterofunctional and either ω-ethyl or ω-n-propyl. The reaction of 3-buten-1-ol with triethylaluminum (Et3Al) or tripropylaluminum (nPr3Al) in the presence of (NMI)2ZrCl2 and isobutylaluminoxane gave, after protonolysis, (R)-3-methyl-1-pentanol as well as (R)- and (S)-3-methyl-1-hexanols in 88–92% yield in 90–92% enantiomeric excess in one step. These 3-monomethyl-1-alkanols were then converted to two stereoisomers each of 2,4-dimethyl-1-hexanols and 2,4-dimethyl-1-heptanols via methylalumination catalyzed by (NMI)2ZrCl2 and methylaluminoxane followed by oxidation with O2. The four-step (or three-isolation-step) protocol provided syn-2,4-dimethyl-1-alkanols of ≥98% stereoisomeric purity in ≈50% overall yields, whereas (2S,4R)-2,4-dimethyl-1-hexanol of comparable purity was obtained in 40% overall yield. Commercial availability of (S)-2-methyl-1-butanol as a relatively inexpensive material suggested its use in the synthesis of (2S,4S)- and (2R,4S)-2,4-dimethyl-1-hexanols via a three-step protocol consisting of (i) iodination, (ii) zincation followed by Pd-catalyzed vinylation, and (iii) Zr-catalyzed methylalumination followed by oxidation with O2. This three-step protocol is iterative and applicable to the synthesis of reduced polypropionates containing three or more branching methyl groups, rendering this method for the synthesis of reduced polypropionates generally applicable. Its synthetic utility has been demonstrated by preparing the side chain of zaragozic acid A and the C11–C20 fragment of antibiotics TMC-151 A–F. PMID:15073327

  12. Predominance of biotic over abiotic formation of halogenated hydrocarbons in hypersaline sediments in Western Australia.

    Science.gov (United States)

    Ruecker, A; Weigold, P; Behrens, S; Jochmann, M; Laaks, J; Kappler, A

    2014-08-19

    Volatile halogenated organic compounds (VOX) contribute to ozone depletion and global warming. There is evidence of natural VOX formation in many environments ranging from forest soils to salt lakes. Laboratory studies have suggested that VOX formation can be chemically stimulated by reactive Fe species while field studies have provided evidence for direct biological (enzymatic) VOX formation. However, the relative contribution of abiotic and biotic processes to global VOX budgets is still unclear. The goals of this study were to quantify VOX release from sediments from a hypersaline lake in Western Australia (Lake Strawbridge) and to distinguish between the relative contributions of biotic and abiotic VOX formation in microbially active and sterilized microcosms. Our experiments demonstrated that the release of organochlorines from Lake Strawbridge sediments was mainly biotic. Among the organochlorines detected were monochlorinated, e.g., chloromethane (CH3Cl), and higher chlorinated VOX compounds such as trichloromethane (CHCl3). Amendment of sediments with either Fe(III) oxyhydroxide (ferrihydrite) or a mixture of lactate/acetate or both ferrihydrite and lactate/acetate did not stimulate VOX formation. This suggests that although microbial Fe(III) reduction took place, there was no stimulation of VOX formation via Fe redox transformations or the formation of reactive Fe species under our experimental conditions. PMID:25073729

  13. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    Science.gov (United States)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  14. The Eocene Rusayl Formation, Oman, carbonaceous rocks in calcareous shelf sediments: Environment of deposition, alteration and hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Dill, H.G.; Wehner, H.; Kus, J. [Federal Institute for Geosciences and Natural Resources, P.O. Box 510163, D-30631 Hannover (Germany); Botz, R. [University Kiel, Geological-Paleontological Department, Olshausenstrasse 40-60, D-24118 Kiel (Germany); Berner, Z.; Stueben, D. [Technical University Karlsruhe, Institute for Mineralogy and Geochemistry, Fritz-Haber-Weg 2, D-76131 Karlsruhe (Germany); Al-Sayigh, A. [Sultan Qaboos University, Geological Dept. PO Box 36, Al-Khod (Oman)

    2007-10-01

    incursions make up a greater deal of the sedimentary record than mangrove swamps. Terra rossa paleosols mark the end of accumulation of organic material (OM) and herald supratidal conditions at the passage of Rusayl Formation into the overlying Seeb Formation. In the subtidal-supratidal cycles of lithofacies unit VIII the terra rossa horizons are thining upwards and become gradually substituted for by deep-water middle ramp sediments of lithofacies unit IX. Framboidal pyrite, (ferroan) dolomite with very little siderite are indicative of an early diagenetic alteration stage I under rather moderate temperatures of formation. During a subsequent stage II, an increase in the temperature of alteration was partly induced by burial and a high heat flow from the underlying Semail Ophiolite. Type-III kerogen originating from higher plants and, in addition, some marine biota gave rise to the generation of small amounts of soluble organic matter during this stage of diagenesis. The average reflectance of humic particles marks the beginning of the oil window and the production index reveals the existence of free hydrocarbons. Further uplift of the Eocene strata and oxidation during stage IIII caused veins of satin spar to form from organic sulfur and pyrite in the carbonaceous material. Lowering of the pH value of the pore fluid led to the precipitation of jarosite and a set of hydrated aluminum sulfates dependant upon the cations present in the wall rocks. AMD minerals (= acid mine drainage) are not very widespread in this carbonaceous series intercalated among calcareous rocks owing to the buffering effect of carbonate minerals. These carbonate-hosted carbonaceous rocks are below an economic level as far as the mining of coal is concerned, but deserves particular attention as source rocks for hydrocarbons in the Middle East, provided a higher stage of maturity is reached. (author)

  15. The Molybdenum Active Site of Formate Dehydrogenase Is Capable of Catalyzing C-H Bond Cleavage and Oxygen Atom Transfer Reactions.

    Science.gov (United States)

    Hartmann, Tobias; Schrapers, Peer; Utesch, Tillmann; Nimtz, Manfred; Rippers, Yvonne; Dau, Holger; Mroginski, Maria Andrea; Haumann, Michael; Leimkühler, Silke

    2016-04-26

    Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal-containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pKa of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase. PMID:27054466

  16. Low-maturity Kulthieth Formation coal: A possible source of polycyclic aromatic hydrocarbons in benthic sediment of the northern Gulf of Alaska

    Energy Technology Data Exchange (ETDEWEB)

    Van Kooten, G.K.; Short, J.W.; Kolak, J.J. [Calvin College, Grand Rapids, MI (United States). Dept. of Geology, Geography & Environmental Studies

    2002-07-01

    The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH:TOC) for Bering River coal field (BRCF) sources are too low; i.e. the coals are over mature to be consistent with GOA sediments. Evidence is presented that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH:TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature.

  17. Evidence from SOFIA Imaging of Polycyclic Aromatic Hydrocarbon Formation along a Recent Outflow in NGC 7027

    Science.gov (United States)

    Lau, Ryan M.; Werner, Michael W.; Sahai, Raghvendra; Ressler, Michael E.

    2016-06-01

    We report spatially resolved (FWHM ~ 3.8 - 4.6'') mid-IR imaging observations of the planetary nebula (PN) NGC 7027 taken with the 2.5-m telescope aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Images of NGC 7027 were acquired at 6.3, 6.6, 11.1, 19.7, 24.2, 33.6, and 37.1 μm using the Faint Object Infrared Camera for the SOFIA Telescope (FORCAST). The observations reveal emission from Polycyclic Aromatic Hydrocarbon (PAH) and warm dust (TD ~ 90 K) from the ionized inner edge of the molecular envelope surrounding the central star of the planetary nebula (CSPN). The DustEM code was used to fit the spectral energy distribution of fluxes obtained by FORCAST and the archival infrared spectrum of NGC 7027 acquired by the Short Wavelength Spectrometer (SWS) on the Infrared Space Observatory (ISO). Best-fit dust models reveal a total dust mass of ~6 × 10-3 M⊙, where carbonaceous large (a = 1.5 μm) and very small (a ~ 12 Å) grains, and PAHs (3.1 Å photo-dissociation region (PDR) and molecular envelope.

  18. Evidence from SOFIA Imaging of Polycyclic Aromatic Hydrocarbon Formation along a Recent Outflow in NGC 7027

    CERN Document Server

    Lau, R M; Sahai, R; Ressler, M E

    2016-01-01

    We report spatially resolved (FWHM$\\sim3.8-4.6"$) mid-IR imaging observations of the planetary nebula (PN) NGC 7027 taken with the 2.5-m telescope aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Images of NGC 7027 were acquired at 6.3, 6.6, 11.1, 19.7, 24.2, 33.6, and 37.1 $\\mu\\mathrm{m}$ using the Faint Object Infrared Camera for the SOFIA Telescope (FORCAST).The observations reveal emission from Polycyclic Aromatic Hydrocarbon (PAH) and warm dust ($T_D\\sim90$ K) from the illuminated inner edge of the molecular envelope surrounding the ionized gas and central star. The DustEM code was used to fit the spectral energy distribution of fluxes obtained by FORCAST and the archival infrared spectrum of NGC 7027 acquired by the Short Wavelength Spectrometer (SWS) on the Infrared Space Observatory (ISO). Best-fit dust models provide a total dust mass of $5.8^{+2.3}_{-2.6}\\times10^{-3}$ $\\mathrm{M}_\\odot$, where carbonaceous large ($a=1.5$ $\\mu$m) and very small ($a \\sim12\\AA$) grains, and PAHs ($...

  19. Formation of oxides of nitrogen in monodisperse spray combustion of hydrocarbon fuels

    Science.gov (United States)

    Nizami, A. A.; Singh, S.; Cernansky, N. P.

    1982-01-01

    Experimental results of exit plane NO/NO(x) emissions from atmospheric monodisperse fuel spray combustion are presented. Six different hydrocarbon fuels were studied: isopropanol, n-propanol, n-octane, iso-octane, n-heptane and methanol. The results indicate an optimum droplet size for minimizing NO/NO(x) production for all of the test fuels. At the optimum droplet diameter, reductions in NO/NO(x) relative to the NO(x) occurred at droplet diameters of 55 and 48 microns respectively, as compared to a 50-micron droplet size for isopropanol. The occurrence of the minimum NO(x) point at different droplet diameters for the different fuels appears to be governed by the extent of prevaporization of the fuel in the spray, and is consistent with theoretical calculations based on each fuel's physical properties. Estimates are also given for the behavior of heavy fuels and of polydisperse fuel sprays in shifting the minimum NO(x) point compared to a monodisperse situation.

  20. Modeling unburned hydrocarbon formation due to absorption/desorption processes into the wall oil film

    International Nuclear Information System (INIS)

    This paper reports that as a result of continuing air pollution problems, very stringent regulations are being enforced to control emissions of unburned hydrocarbons (HC) from premixed-charge, spark-ignition engines. A number of attempts have been reported on modeling sources of HC emissions using various analytical tools. Over the past decade, the development of multi-dimensional reacting flow codes has advanced considerably. Perhaps the most widely used multi-dimensional engine simulation code is KIVA-II, which was developed at Lost Alamos National Laboratory. The ability to deal with moving boundary conditions caused by the piston movement is built in this code. This code also includes models for turbulent fluid flow, turbulent interaction between spray drops and gas, heat transfer, chemical reaction, and fuel spray. A standard k-ε turbulence model is used for gas flow. The fuel spray model is based on the stochastic particle technique, and includes sub-models for droplet injection, breakup, collision and coalescence, and evaporation

  1. Method for the control of solids accompanying hydrocarbon production from subterranean formations

    Energy Technology Data Exchange (ETDEWEB)

    Strubhar, M.K.; Healy, J.C.

    1992-04-21

    This patent describes a method for controlling solids contained in hydrocarbonaceous fluids produced from a subterranean formation. It comprises perforating a wellbore at a productive interval of a hydrocarbonaceous fluid-containing formation; injecting into the productive interval via perforations a fracturing fluid containing a resin-coated self-consolidating particulate material which is of a size and composition sufficient to prop a created fracture and form a permeable consolidated mass therein; fracturing hydraulically the productive interval and thereafter creating a propped fracture with a self-consolidated permeable mass therein as well as within the perforations and wellbore which mass has filtration properties and composition sufficient to restrain solids entrained in the hydrocarbonaceous fluid; and removing mechanically the consolidated permeable mass from the wellbore which allows hydrocarbonaceous fluids to be produced from the formation substantially solids free which solids are restrained by the permeable consolidated mass within the fracture and perforations.

  2. Temperature control of pattern formation in the Ru(bpy)(3)(2+)-catalyzed BZ-AOT system.

    Science.gov (United States)

    McIlwaine, Rachel; Vanag, Vladimir K; Epstein, Irving R

    2009-03-14

    Using temperature as a control parameter, we observe a transition from stationary Turing patterns at T = 15-20 degrees C to traveling waves at T = 50 degrees C (and above) in the Ru(bpy)(3)(2+)-catalyzed Belousov-Zhabotinsky (BZ) reaction incorporated into the water nanodroplets of a water-in-oil aerosol OT (AOT) microemulsion. At constant chemical composition, molar ratio and droplet fraction, the transition takes place via a series of stable patterns, including oscillatory Turing patterns (at 35-40 degrees C) and reversed oscillatory Turing patterns (at 50 degrees C). We attribute the pattern transitions to a temperature-induced percolation transition of the BZ-AOT microemulsion, implying a change from isolated water nanodroplets to a system-spanning network of water channels. PMID:19240935

  3. Unraveling the Timing of Fluid Migration and Trap Formation in the Brooks Range Foothills: A Key to Discovering Hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Catherine L. Hanks

    2008-12-31

    Naturally occurring fractures can play a key role in the evolution and producibility of a hydrocarbon accumulation. Understanding the evolution of fractures in the Brooks Range/Colville basin system of northern Alaska is critical to developing a better working model of the hydrocarbon potential of the region. This study addressed this problem by collecting detailed and regional data on fracture distribution and character, structural geometry, temperature, the timing of deformation along the Brooks Range rangefront and adjacent parts of the Colville basin, and the in situ stress distribution within the Colville basin. This new and existing data then were used to develop a model of how fractures evolved in northern Alaska, both spatially and temporally. The results of the study indicate that fractures formed episodically throughout the evolution of northern Alaska, due to a variety of mechanisms. Four distinct fracture sets were observed. The earliest fractures formed in deep parts of the Colville basin and in the underlying Ellesmerian sequence rocks as these rocks experienced compression associated with the growing Brooks Range fold-and-thrust belt. The orientation of these deep basin fractures was controlled by the maximum in situ horizontal stress in the basin at the time of their formation, which was perpendicular to the active Brooks Range thrust front. This orientation stayed consistently NS-striking for most of the early history of the Brooks Range and Colville basin, but changed to NW-striking with the development of the northeastern Brooks Range during the early Tertiary. Subsequent incorporation of these rocks into the fold-and-thrust belt resulted in overprinting of these deep basin fractures by fractures caused by thrusting and related folding. The youngest fractures developed as rocks were uplifted and exposed. While this general order of fracturing remains consistent across the Brooks Range and adjacent Colville basin, the absolute age at any one

  4. Two herbivore-induced cytochrome P450 enzymes CYP79D6 and CYP79D7 catalyze the formation of volatile aldoximes involved in poplar defense.

    Science.gov (United States)

    Irmisch, Sandra; McCormick, Andrea Clavijo; Boeckler, G Andreas; Schmidt, Axel; Reichelt, Michael; Schneider, Bernd; Block, Katja; Schnitzler, Jörg-Peter; Gershenzon, Jonathan; Unsicker, Sybille B; Köllner, Tobias G

    2013-11-01

    Aldoximes are known as floral and vegetative plant volatiles but also as biosynthetic intermediates for other plant defense compounds. While the cytochrome P450 monooxygenases (CYP) from the CYP79 family forming aldoximes as biosynthetic intermediates have been intensively studied, little is known about the enzymology of volatile aldoxime formation. We characterized two P450 enzymes, CYP79D6v3 and CYP79D7v2, which are involved in herbivore-induced aldoxime formation in western balsam poplar (Populus trichocarpa). Heterologous expression in Saccharomyces cerevisiae revealed that both enzymes produce a mixture of different aldoximes. Knockdown lines of CYP79D6/7 in gray poplar (Populus × canescens) exhibited a decreased emission of aldoximes, nitriles, and alcohols, emphasizing that the CYP79s catalyze the first step in the formation of a complex volatile blend. Aldoxime emission was found to be restricted to herbivore-damaged leaves and is closely correlated with CYP79D6 and CYP79D7 gene expression. The semi-volatile phenylacetaldoxime decreased survival and weight gain of gypsy moth (Lymantria dispar) caterpillars, suggesting that aldoximes may be involved in direct defense. The wide distribution of volatile aldoximes throughout the plant kingdom and the presence of CYP79 genes in all sequenced genomes of angiosperms suggest that volatile formation mediated by CYP79s is a general phenomenon in the plant kingdom. PMID:24220631

  5. Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

    Directory of Open Access Journals (Sweden)

    Damien Hédou

    2016-06-01

    Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.

  6. Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

    Directory of Open Access Journals (Sweden)

    Rajendra Surasani

    2012-11-01

    Full Text Available Simple and efficient procedures for palladium-catalyzed cross-coupling reactions of N-substituted 4-bromo-7-azaindole (1H-pyrrole[2,3-b]pyridine, with amides, amines, amino acid esters and phenols through C–N and C–O bond formation have been developed. The C–N cross-coupling reaction of amides, amines and amino acid esters takes place rapidly by using the combination of Xantphos, Cs2CO3, dioxane and palladium catalyst precursors Pd(OAc2/Pd2(dba3. The combination of Pd(OAc2, Xantphos, K2CO3 and dioxane was found to be crucial for the C–O cross-coupling reaction. This is the first report on coupling of amides, amino acid esters and phenols with N-protected 4-bromo-7-azaindole derivatives.

  7. Hydrocarbon pneumonia

    Science.gov (United States)

    Pneumonia - hydrocarbon ... Coughing Fever Shortness of breath Smell of a hydrocarbon product on the breath Stupor (decreased level of ... Most children who drink or inhale hydrocarbon products and develop ... hydrocarbons may lead to rapid respiratory failure and death.

  8. Formation of unsaturated hydrocarbons in interstellar ice analogs by cosmic rays

    OpenAIRE

    Pilling, S.; Andrade, D. P. P; da Silveira, E. F.; Rothard, H.; Domaracka, A.; Boduch, P.

    2012-01-01

    The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accel\\'erat\\'eur National d'Ions Lourds) ...

  9. The paleoclimatic records and the relevance with the formation of hydrocarbon source rocks:A case study of Huanghekou depression,Bohaiwan basin

    Institute of Scientific and Technical Information of China (English)

    Zhanhong LIU; Sitian LI; Renchen XIN; Changgui XU; Jianchun CHENG

    2008-01-01

    Bohaiwan basin,covering an area of 200 000 km2,is one of the most important oil-bearing basins in Eastern China.Rifting processes formed the basin,and two evolution phases can be recognized.The rifting phase developed in Paleogene,and post-rifting phase occurred in Neogene.More than 200 oil fields have been found in the onshore and offshore area in Bohaiwan basin in recent years.The distribution of the oil fields is closely related to the rich hydrocarbon depressions,and the Huanghekou depression is one of these rich hydrocarbon depressions.A number of large and medium-sized oil and gas fields have been found in this area,such as BZ25-1,BZ34 etc.,and the hydrocarbon was mainly from the Huanghekou depression.The formation of rich hydrocarbon source rocks depended on the tectonic setting of rapid subsidence,favorable paleoclimatic conditions and paleolimnology environments.The effects of paleoclimatic condition on hydrocarbon source rocks are the focus of this paper.

  10. Formation of hydrocarbons from carbon monoxide on rhodium/alumina model catalysts

    International Nuclear Information System (INIS)

    When tunnel junctions containing carbon monoxide adsorbed on alumina-supported Rh are heated in hydrogen the vibrational peaks due to carbon monoxide decrease and a new set of vibrational peaks grows. Shifts in the positions of some of these new peaks are observed if the normal 12C16O is replaced by 13C16O, but not if it is replaced by 12C18O. This suggests that the new surface species includes the carbon from the CO, but not the oxygen. The set of new peaks grows together and is in one-to-one correspondence with the peaks of ethylidene as extrapolated between published spectra of halogenated derivatives. A different surface species, tentatively identified as formate ions, can be produced by heating without hydrogen. 33 references, 4 figures, 1 table

  11. PHOTON-INDUCED FORMATION OF MOLECULAR HYDROGEN FROM A NEUTRAL POLYCYCLIC AROMATIC HYDROCARBON: 9,10-DIHYDROANTHRACENE

    Energy Technology Data Exchange (ETDEWEB)

    Fu Yi; Szczepanski, Jan; Polfer, Nick C., E-mail: polfer@chem.ufl.edu [Department of Chemistry and Center for Chemical Physics, University of Florida, P.O. Box 117200, Gainesville, FL 32611-7200 (United States)

    2012-01-01

    Experimental results from infrared spectroscopy and mass spectrometry provide compelling evidence that UV irradiation of the neutral polycyclic aromatic hydrocarbon (PAH) 9,10-dihydroanthracene (DHA), trapped in solid argon (12 K), results in efficient (i.e., 90% yield) conversion to anthracene and molecular hydrogen. A number of dissociation pathways involving single or double hydrogen loss are investigated computationally. Among these, two mechanisms are most credible for a one-photon dissociation process involving UV photons <5.5 eV. For the lowest-energy pathway (2.3 eV), a simultaneous lengthening of the C-H bonds of H9 and H10 gives rise to an anthracene-H{sub 2} complex. A higher-energy mechanism (3.4 eV) involves an initial lengthening of the H9 C-H bond, followed by this hydrogen 'grabbing' H10, and forming H{sub 2}. The high yield of this photolysis reaction suggests that similar reactions may take place for other neutral PAHs, with implications for the formation of molecular hydrogen in regions of low UV exposure, such as in dark clouds.

  12. A New Star-Formation Rate Calibration from Polycyclic Aromatic Hydrocarbon Emission Features and Application to High Redshift Galaxies

    CERN Document Server

    Shipley, Heath V; Rieke, George H; Brown, Michael J I; Moustakas, John

    2016-01-01

    We calibrate the integrated luminosity from the polycyclic aromatic hydrocarbon (PAH) features at 6.2\\micron, 7.7\\micron\\ and 11.3\\micron\\ in galaxies as a measure of the star-formation rate (SFR). These features are strong (containing as much as 5-10\\% of the total infrared luminosity) and suffer minimal extinction. Our calibration uses \\spitzer\\ Infrared Spectrograph (IRS) measurements of 105 galaxies at $0 < z < 0.4$, infrared (IR) luminosities of $10^9 - 10^{12} \\lsol$, combined with other well-calibrated SFR indicators. The PAH luminosity correlates linearly with the SFR as measured by the extinction-corrected \\ha\\ luminosity over the range of luminosities in our calibration sample. The scatter is 0.14 dex comparable to that between SFRs derived from the \\paa\\ and extinction-corrected \\ha\\ emission lines, implying the PAH features may be as accurate a SFR indicator as hydrogen recombination lines. The PAH SFR relation depends on gas-phase metallicity, for which we supply an empirical correction for...

  13. Enhanced reactivity of hydroxylated polycyclic aromatic hydrocarbons to birnessite in soil: reaction kinetics and nonextractable residue formation.

    Science.gov (United States)

    Jung, Jae-Woong; Lee, Seunghwan; Ryu, Hyerim; Nam, Kyoungphile; Kang, Ki-Hoon

    2008-05-01

    Phenanthrene and pyrene were not transformed by birnessite (delta-MnO2) in the presence of phenol. The phenoxy radicals generated from phenol by birnessite did not act as a mediator for polycyclic aromatic hydrocarbon radical reaction under the studied conditions. In contrast, 9-hydroxyphenanthrene and 1-hydroxypyrene were remarkably sensitive to birnessite. The disappearance patterns of the test compounds both in the aqueous phase and soil followed first-order kinetics, with a linear relationship found between the rate constants and the surface area of birnessite. Moreover, the data indicated that the reaction was faster in the presence of soil than in the aqueous phase probably because of the presence of hydroxyl groups in soil organic matter. Sequential solvent extraction was not successful in the recovery of 9-hydroxyphenanthrene from the birnessite-treated soil samples, and capillary electrophoresis data suggest the formation of nonextractable residues of the compound in soil. In addition, the acute toxicity determined by Microtox declined approximately 8.3 times in the soil samples treated with birnessite compared to untreated samples, demonstrating that the toxic compound was no longer present as its parent form. PMID:18419188

  14. Formation of unsaturated hydrocarbons in interstellar ice analogs by cosmic rays

    CERN Document Server

    Pilling, S; da Silveira, E F; Rothard, H; Domaracka, A; Boduch, P

    2012-01-01

    The formation of double and triple C-C bonds from the processing of pure c-C6H12 (cyclohexane) and mixed H2O:NH3:c-C6H12 (1:0.3:0.7) ices by highly-charged, and energetic ions (219 MeV O^{7+} and 632 MeV Ni^{24+}) is studied. The experiments simulate the physical chemistry induced by medium-mass and heavy-ion cosmic rays in interstellar ices analogs. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accel\\'erat\\'eur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometry at different ion fluences. Dissociation cross section of cyclohexane and its half-life in astrophysical environments were determined. A comparison between spectra of bombarded ices and young stellar sources indicates that the initial composition of grains in theses environments should contain a mixture of H2O, NH3, CO (or CO2), simple al...

  15. On a revised mechanism of side product formation in the lignin peroxydase catalyzed oxidation of veratryl alcohol

    OpenAIRE

    Have, ten, A.; Franssen, M.C.R.

    2001-01-01

    The O2-dependent formation of side products during the oxidation of veratryl alcohol (VA) by lignin peroxidase has previously been proposed to start with the attack of H2O on the VA radical cation (VA. ). This initial reaction is unlikely since it would also lead to side product formation in the absence of O2, which is not the case. In the current mechanism VA. reacts first with O2, whereafter H2O attacks. Furthermore, this paper describes an alternative explanation for the inhibitory effect ...

  16. The Formation and Distribution of the Marine Hydrocarbon Source Rock in the Tarim Basin, NW China

    Institute of Scientific and Technical Information of China (English)

    CAI Xiyuan; WANG Yi

    2008-01-01

    There are significant differences in type and distribution between marine source rock and continental source rock. According to the lithology, the Cambrian-Ordovician source rock in the Tarim basin is divided into two types: the carbonate source rock and the mud source rock. The two sets of source rocks are developed mainly in three sets of formations, Lower-Middle Cambrian carbonate source rock and mud source rock, Lower-Middle Ordovician mud source rock and Upper Ordovician lime mud source rock. The stratigraphic and areal distributions of the source rocks are controlled by the altitude and the sedimentary facies respectively. The mud source rock is developed in slope-semi deep sea environment. The source rock developed in the slope sedimentary environment is related with the anoxic environment and the one developed in semi deep sea has a close relationship with the up-flowing sea water. The carbonate source rock is developed mainly in platform slope of highstand systems tract and it is usually intimately associated with the salt rock. The Lower-Middle Cambrian carbonate source rock is developed mainly in the Bachu, Tazhong, Taugguzibasi and Yingmaili areas. The Lower-Middle Cambrian mud source rock is mainly developed in the areas east of the line of Kunan 1-Tadong 1. The Lower-Middle Ordovician mud source rock is developed mainly in the east slope of the Manjiaer depression. The carbonate source rock of Early Ordovician is developed mainly in the platform slope of highstand systems tract, such as the south margin of Tabei, the north slope of Tazhong, the Bachu area and Keping area.

  17. Formation of organic solid phases in hydrocarbon reservoir fluids. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, S.I.; Lindeloff, N.; Stenby, E.H.

    1998-12-31

    The occurrence of solid phases during oil recovery is a potential problem. The present work has mainly been concerned with wax formation due to cooling of oils with a large paraffin content. 8 oils have been included in this project, although only a few of these have till now been subject to all the experimental techniques applied. The oils and wax fractions from these have been characterized using techniques such as GC-MS and Ftir. The goal has in part been to get a detailed description of the oil composition for use in model evaluation and development and in part to get a fundamental understanding of waxy oil properties and behaviour. A high pressure (200 bar) equipment has been developed for automatic detection of wax appearance using a filtration technique and laser light turbidimetry. The latter was found to be far superior to the filtration. The filtration was used to sample the incipient solid phase for characterization. However entrapment of liquid in the filters currently used have hampered this part. A number of model systems and one gas condensate have been investigated. The GC-MS procedure was found only to been able to detect molecules up to n-C45 and the group type analysis was not accurate enough for modelling purposes. Using Ftir it was obvious that incipient phases may contain very complex molecules (asphaltenes) which are not captured by GC-MS especially when fractionation is done using the acetone precipitation at elevated temperature. The latter fractionation procedure has been investigated thoroughly as a tool for understanding wax distribution etc. Within thermodynamic modelling a delta lattice parameter model has been developed which incorporates the non-ideality of the solid phases into the calculation of SLE. The non-ideality is estimated from pure component properties. A new algorithm for phase equilibria involving gas-liquid-solid has been developed. Currently both the model work and the experimental works are continued. (au)

  18. Parameters affecting diacylglycerol formation during the production of specific-structured lipids by lipase-catalyzed interesterification

    DEFF Research Database (Denmark)

    Xu, Xuebing; Mu, Huiling; Skands, Anja; Høy, Carl-Erik; Adler-Nissen, Jens

    1999-01-01

    (RSM) to minimize the numbers of experiments. The DAG content of the product was dependent on all parameters examined except reaction time. DAG formation increased with increasing water content, enzyme load, reaction temperature, and substrate ratio. The content of sn-1,3-DAGs was higher than that of...

  19. Radical formation in the [MeReO3]-catalyzed aqueous peroxidative oxidation of alkanes: a theoretical mechanistic study.

    Science.gov (United States)

    Kuznetsov, Maxim L; Pombeiro, Armando J L

    2009-01-01

    Plausible mechanisms of radical formation in the catalytic system [MeReO(3)]/H(2)O(2)/H(2)O-CH(3)CN for the oxidation of alkanes to alcohols and ketones, via radical pathways, are investigated extensively at the density functional theory level. The most favorable route is based on the monoperoxo complex [MeReO(2)(O(2))(H(2)O)] and includes the formation of an H(2)O(2) adduct, water-assisted H-transfer from H(2)O(2) to the peroxo ligand, and generation of HOO(*). The thus formed reduced Re(VI) complex [MeReO(2)(OOH)(H(2)O)] reacts with H(2)O(2), resulting, upon water-assisted H-transfer and O-OH bond homolysis, in the regeneration of the oxo-Re(VII) catalyst and formation of the HO(*) radical that reacts further with the alkane. Water plays a crucial role by (i) stabilizing transition states for the proton migrations and providing easy intramolecular H-transfers in the absence of any N,O-ligands and (ii) saturating the Re coordination sphere what leads to a decrease of the activation barrier for the formation of HOO(*). The activation energy of the radical formation calculated for [MeReO(3)] (17.7 kcal/mol) is compatible with that determined experimentally [Shul'pin et al. J. Chem. Soc., Perkin Trans. 2 2001, 1351 .] for oxo-V-based catalytic systems (17 +/- 2 kcal/mol), and the overall type of mechanism proposed for such V catalysts is also effective for [MeReO(3)]. PMID:19049432

  20. Direct formation of gasoline hydrocarbons from cellulose by hydrothermal conversion with in situ hydrogen

    International Nuclear Information System (INIS)

    A new process based on aqueous-phase dehydration/hydrogenation (APD/H) has been developed to directly produce liquid alkanes (C7–9), which are the main components of fossil gasoline, from cellulose in one single batch reactor without the consumption of external hydrogen (H2). In this new process, part of the cellulose is first converted to in situ H2 by steam reforming (SR) in the steam gas phase mainly; and, in the liquid water phase, cellulose is converted to an alkane precursor, such as 5-(hydroxymethyl)furfural (HMF). In the final reaction step, in situ H2 reacts with HMF to form liquid alkanes through APD/H. Accordingly, this new process has been named SR(H2)-APD/H. Experimental results show that the volumetric ratio of the reactor headspace to the reactor (H/R) and an initial weakly alkaline condition are the two key parameters for SR(H2)-APD/H. With proper H/R ratios (e.g., 0.84) and initial weakly alkaline conditions (e.g., pH = 7.5), liquid alkanes are directly formed from the SR(H2)-APD/H of cellulose using in situ H2 instead of external H2. In this study, compared with pyrolysis and hydrothermal liquefaction of cellulose at the same temperatures with same retetion time, SR(H2)-APD/H greatly increased the liquid alkane yields, by approximately 700 times and 35 times, respectively. Based on this process, direct formation of fossil gasoline from renewable biomass resources without using external H2 becomes possible. -- Highlights: ► A process of producing gasoline alkanes from cellulose was proposed and studied. ► Alkane precursors and in situ H2 were formed simultaneously in a single reactor. ► Alkanes subsequently formed by reactions between in situ H2 and alkane precursors. ► The yields were 700 and 35 times higher than pyrolysis and hydrothermal conversion.

  1. Bispalladacycle-catalyzed Brønsted acid/base-promoted asymmetric tandem azlactone formation-Michael addition.

    Science.gov (United States)

    Weber, Manuel; Jautze, Sascha; Frey, Wolfgang; Peters, René

    2010-09-01

    Cooperative activation by a soft bimetallic catalyst, a hard Brønsted acid, and a hard Brønsted base has allowed the formation of highly enantioenriched, diastereomerically pure masked alpha-amino acids with adjacent quaternary and tertiary stereocenters in a single reaction starting from racemic N-benzoylated amino acids. The products can, for example, be used to prepare bicyclic dipeptides. PMID:20715774

  2. Generation of hydrocarbon gases in modern sedimentary and volcanogenic sedimentary formations of the eastern and southern parts of the Atlantic Ocean

    Energy Technology Data Exchange (ETDEWEB)

    Veber, V.V.; Sazonov, M.L.; Morozova, S.N.; Gershanovich, D.E.; Zarikhin, I.P.; Chernov, V.I.

    1977-01-01

    A study is made of contemporary gas formation based on data on valcano-genic-sedimentary layers of the southern part of the Atlantic and carbon layers of the eastern part of the Atlantic as well as terrigenous residues of the Skoskh Sea. A broad range of deposit facies was established in which there occurs a natural generation of gaseous hydrocarbons (including those heavier than methane). 2 figures, 2 tables.

  3. Does glucose enhance the formation of nitrogen containing polycyclic aromatic compounds and polycyclic aromatic hydrocarbons in the pyrolysis of proline?

    Energy Technology Data Exchange (ETDEWEB)

    Phillip F. Britt; A.C. Buchanan; Clyde V. Owens, Jr.; J. Todd Skeen [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Chemical and Analytical Sciences Division

    2004-08-01

    The gas-phase pyrolysis of proline, glucose, 1-((2{prime}-carboxy)pyrrolidinyl)-1-deoxy-D-fructose (the proline Amadori compound), and a 1:1 mixture by weight of proline and glucose was investigated at high temperatures (600-840{sup o}C) and short residence time (i.e. 1.0 s) in an inert atmosphere to determine if glucose or Maillard reaction products enhance the formation of nitrogen containing polycyclic aromatic compounds (N-PACs) and polycyclic aromatic hydrocarbons (PAHs) in the pyrolysis of proline. To study the gas-phase formation of N-PACs and PAHs, the substrates were sublimed into the pyrolysis furnace at 460{sup o}C. Thermogravimetric analysis showed that glucose, the proline/glucose mixture, and the proline Amadori compound undergo solid-state decomposition reactions before subliming. Thus, the substrates were pyrolyzed in two stages: at 460{sup o}C during the sublimation and at 600-840{sup o}C. At 800{sup o}C with a residence time of 1.0 s, proline produced low yields of N-PACs, such as quinoline, isoquinoline, indole, acridine, and carbazole, and PAHs, such as phenanthrene, pyrene, benz(a)anthracene, benzofluoranthene isomers, and benzo(a)pyrene. Increasing the temperature and residence time increased the yield of these products. Under similar pyrolysis conditions, the proline Amadori compound produced 2-8 fold more N-PACs and PAHs than proline. A 1:1 mixture of proline and glucose produced a similar slate of pyrolysis products as the proline Amadori compound, but it is unclear whether the proline Amadori compound was an intermediate in the reaction. In general, the proline Amadori compound produced a higher yield of N-PACs and PAHs than the proline/glucose mixture, but glucose clearly enhances the low temperature gas-phase formation of N-PACs and PAHs from the pyrolysis of proline. 56 refs., 10 figs., 3 tabs.

  4. Non-methane hydrocarbons (NMHCs) and their contribution to ozone formation potential in a petrochemical industrialized city, Northwest China

    Science.gov (United States)

    Jia, Chenhui; Mao, Xiaoxuan; Huang, Tao; Liang, Xiaoxue; Wang, Yanan; Shen, Yanjie; Jiang, Wanyanhan; Wang, Huiqin; Bai, Zhilin; Ma, Minquan; Yu, Zhousuo; Ma, Jianmin; Gao, Hong

    2016-03-01

    Hourly air concentrations of fifty-three non-methane hydrocarbons (NMHCs) were measured at downtown and suburb of Lanzhou, a petrochemical industrialized city, Northwest China in 2013. The measured data were used to investigate the seasonal characteristics of NMHCs air pollution and their contributions to the ozone formation in Lanzhou. Annually averaged NMHCs concentration was 38.29 ppbv in downtown Lanzhou. Among 53 NMHCs, alkanes, alkenes, and aromatics accounted for 57%, 23% and 20% of the total NMHCs air concentration, respectively. The atmospheric levels of toluene and propane with mean values of 4.62 and 4.56 ppbv were higher than other NMHCs, respectively. The ambient levels of NMHCs in downtown Lanzhou were compared with measured NMHCs data collected at a suburban site of Lanzhou, located near a large-scale petrochemical industry. Results show that the levels of alkanes, alkenes, and aromatics in downtown Lanzhou were lower by factors of 3-11 than that in west suburb of the city. O3-isopleth plots show that ozone was formed in VOCs control area in downtown Lanzhou and NOx control area at the west suburban site during the summertime. Propylene-equivalent (Prop-Equiv) concentration and the maximum incremental reactivity (MIR) in downtown Lanzhou indicate that cis-2-butene, propylene, and m/p-xylene were the first three compounds contributing to ozone formation potentials whereas in the petrochemical industrialized west suburb, ethane, propene, and trans-2-Butene played more important role in the summertime ozone formation. Principal component analysis (PCA) and multiple linear regression (MLR) were further applied to identify the dominant emission sources and examine their fractions in total NMHCs. Results suggest that vehicle emission, solvent usage, and industrial activities were major sources of NMHCs in the city, accounting for 58.34%, 22.19%, and 19.47% of the total monitored NMHCs in downtown Lanzhou, respectively. In the west suburb of the city

  5. Separation of levan-formation and sucrose-hydrolysis catalyzed by levansucrase of Zymomonas mobilis using in vitro mutagenesis

    OpenAIRE

    G. Sangiliyandi; T R Kannan; K. Chandra Raj; P.GunaSekaran

    1999-01-01

    A levansucrase (SacB) of Zymomonas mobilis capable of sucrose hydrolysis but not levan formation was isolated through invitro mutagenesis of cloned sacB gene. When the sacB mutant gene was expressed in Escherichiacoli strains, only 50% of the sucrose-hydrolysing activity (2.0 U/mg) was produced, compared to the wild type levansucrase (4.0 U/mg). Sequencing of the sacB mutant gene revealed changes of two amino acid residues (Phe-102 to Leu and Trp-261 to Lys in the levansucrase). The absence o...

  6. THE 3.3 μm POLYCYCLIC AROMATIC HYDROCARBON EMISSION AS A STAR FORMATION RATE INDICATOR

    International Nuclear Information System (INIS)

    Polycyclic aromatic hydrocarbon (PAH) emission features dominate the mid-infrared spectra of star-forming galaxies and can be useful to calibrate star formation rates (SFRs) and diagnose ionized states of grains. However, the PAH 3.3 μm feature has not been studied as much as other PAH features since it is weaker than others and resides outside of Spitzer capability. In order to detect and calibrate the 3.3 μm PAH emission and investigate its potential as an SFR indicator, we carried out an AKARI mission program, AKARI mJy Unbiased Survey of Extragalactic Sources (AMUSES), and compared its sample with various literature samples. We obtained 2-5 μm low-resolution spectra of 20 flux-limited galaxies with mixed spectral energy distribution classes, which yielded the detection of the 3.3 μm PAH emission from 3 out of 20 galaxies. For the combined sample of AMUSES and literature samples, the 3.3 μm PAH luminosities correlate with the infrared luminosities of star-forming galaxies, albeit with a large scatter (1.5 dex). The correlation appears to break down at the domain of ultraluminous infrared galaxies (ULIRGs), and the power of the 3.3 μm PAH luminosity as a proxy for the infrared luminosity is hampered at log[L PAH3.3 erg–1 s–1] > ∼42.0. Possible origins for this deviation in the correlation are discussed, including contributions from active galactic nuclei and strongly obscured young stellar objects, and the destruction of PAH molecules in ULIRGs.

  7. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu; Lin, Ying-Hsuan; Bhathela, Neil A.; Ortega, John; Worton, David; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Gold, Avram; Surratt, Jason D.

    2014-04-08

    Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.

  8. Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs.

    Science.gov (United States)

    Perez, Felix; Oda, Susumu; Geary, Laina M; Krische, Michael J

    2016-06-01

    Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition. PMID:27573275

  9. Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles.

    Science.gov (United States)

    Chu, Crystal K; Liang, Yufan; Fu, Gregory C

    2016-05-25

    A wide array of cross-coupling methods for the formation of C-C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C-heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C-Si bonds. In this study, we address this challenge, establishing that a simple, commercially available nickel catalyst (NiBr2·diglyme) can achieve couplings of alkyl bromides with nucleophilic silicon reagents under unusually mild conditions (e.g., -20 °C); especially noteworthy is our ability to employ unactivated tertiary alkyl halides as electrophilic coupling partners, which is still relatively uncommon in the field of cross-coupling chemistry. Stereochemical, relative reactivity, and radical-trap studies are consistent with a homolytic pathway for C-X bond cleavage. PMID:27187869

  10. Separation of levan-formation and sucrose-hydrolysis catalyzed by levansucrase of Zymomonas mobilis using in vitro mutagenesis

    Directory of Open Access Journals (Sweden)

    G. Sangiliyandi

    1999-01-01

    Full Text Available A levansucrase (SacB of Zymomonas mobilis capable of sucrose hydrolysis but not levan formation was isolated through invitro mutagenesis of cloned sacB gene. When the sacB mutant gene was expressed in Escherichiacoli strains, only 50% of the sucrose-hydrolysing activity (2.0 U/mg was produced, compared to the wild type levansucrase (4.0 U/mg. Sequencing of the sacB mutant gene revealed changes of two amino acid residues (Phe-102 to Leu and Trp-261 to Lys in the levansucrase. The absence of mutation at the site of Cys of SacB is contradictory to the inhibition kinetics that demonstrated the involvement of Cys in conferring the levan-forming activity to the SacB. The present finding is useful in understanding the mechanism of selective modulation of levan-forming (polymerase activity of levansucrase.Um levansucrase (SacB do Zymomonas mobilis capaz de hidrolisar a sucrose mas não de produzir levan foi isolado completamente in vitro, do gene clonado de sacB. Quando o gene do mutante sacB foi expressado em cadeias de Escherichia coli, somente 50% da atividade sucrose-hydrolysing (2,0 U/mg foi produzida, comparado ao levansucrase tipo selvagem 4,0 U/mg. Sequência do sacB (gene mutante revelou mudanças de dois resíduos do amino-ácido (Phe-102 ao Leu e Trp-261 ao Lys no levansucrase. A ausência de mutação no local do Cys de SacB é contraditória à inibição do cinética que demonstrou a participação da Cys em conferir a atividade de formação do levan ao SacB. A presenta descoberta é útil ao entendimento do mecanismo da modulação seletiva da formação do levan (polymerase atividade do levansucrase.

  11. A 4D Synchrotron X-Ray-Tomography Study of the Formation of Hydrocarbon- Migration Pathways in Heated Organic-Rich Shale

    Energy Technology Data Exchange (ETDEWEB)

    Hamed Panahi; Paul Meakin; Francois Renard; Maya Kobchenko; Julien Scheibert; Adriano Mazzini; Bjorn Jamtveit; Anders Malthe-Sorenssen; Dag Kristian Dysthe

    2013-04-01

    Recovery of oil from oil shales and the natural primary migration of hydrocarbons are closely related processes that have received renewed interest in recent years because of the ever tightening supply of conventional hydrocarbons and the growing production of hydrocarbons from low-permeability tight rocks. Quantitative models for conversion of kerogen into oil and gas and the timing of hydrocarbon generation have been well documented. However, lack of consensus about the kinetics of hydrocarbon formation in source rocks, expulsion timing, and how the resulting hydrocarbons escape from or are retained in the source rocks motivates further investigation. In particular, many mechanisms have been proposed for the transport of hydrocarbons from the rocks in which they are generated into adjacent rocks with higher permeabilities and smaller capillary entry pressures, and a better understanding of this complex process (primary migration) is needed. To characterize these processes, it is imperative to use the latest technological advances. In this study, it is shown how insights into hydrocarbon migration in source rocks can be obtained by using sequential high-resolution synchrotron X-ray tomography. Three-dimensional images of several immature "shale" samples were constructed at resolutions close to 5 um. This is sufficient to resolve the source-rock structure down to the grain level, but very-fine-grained silt particles, clay particles, and colloids cannot be resolved. Samples used in this investigation came from the R-8 unit in the upper part of the Green River shale, which is organic rich, varved, lacustrine marl formed in Eocene Lake Uinta, USA. One Green River shale sample was heated in situ up to 400 degrees C as X-ray-tomography images were recorded. The other samples were scanned before and after heating at 400 degrees C. During the heating phase, the organic matter was decomposed, and gas was released. Gas expulsion from the low-permeability shales was coupled

  12. Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

    Directory of Open Access Journals (Sweden)

    Yoshinori Kadoma

    2012-05-01

    Full Text Available The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs between the base-catalyzed hydrolysis rate constants (k1 or the rate constant with glutathione (GSH (log kGSH for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ or heat of formation (Hf calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93, but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89. By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99, but not to Hf. These findings indicate that the 13C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.

  13. Formation of Combustible Hydrocarbons and H2 during Photocatalytic Decomposition of Various Organic Compounds under Aerated and Deaerated Conditions

    OpenAIRE

    Sylwia Mozia; Aleksandra Kułagowska; Morawski, Antoni W.

    2014-01-01

    A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence...

  14. PASSIVE SAMPLING COUPLED TO ULTRAVIOLET IRRADIATION: A USEFUL ANALYTICAL APPROACH FOR STUDYING OXYGENATED POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN BIOAVAILABLE MIXTURES

    OpenAIRE

    Forsberg, Norman D.; O'Connell, Steven G; Allan, Sarah E.; Anderson, Kim A.

    2013-01-01

    The authors investigated coupling passive sampling technologies with ultraviolet irradiation experiments to study polycyclic aromatic hydrocarbon (PAH) and oxygenated PAH transformation processes in real-world bioavailable mixtures. Passive sampling device (PSD) extracts were obtained from coastal waters impacted by the Deepwater Horizon oil spill and Superfund sites in Portland, Oregon, USA. Oxygenated PAHs were found in the contaminated waters with our PSDs. All mixtures were subsequently e...

  15. Modern Processes of Hydrocarbon Migration and Re-Formation of Oil and Gas Fields (Based on the Results of Monitoring and Geochemical Studies)

    Science.gov (United States)

    Plotnikova, Irina; Salakhidinova, Gulmira; Nosova, Fidania; Pronin, Nikita; Ostroukhov, Sergey

    2015-04-01

    Special geochemical studies of oils allowed to allocate a movable migration component of oils in the industrial oil deposits. In the field the migration component of oils varies in different parts of the field. The largest percentage of the light migration component (gas condensate of the oil) was detected in the central part of the Kama-Kinel troughs system. Monitoring of the composition of water, oil and gas (condensate light oil component) in the sedimentary cover and ni crystalline basement led to the conclusion of modern migration of hydrocarbons in sedimentary cover. This proves the existence of the modern processes of formation and reformation of oil and gas fields. This presentation is dedicated to the problem of definition of geochemical criteria of selection of hydrocarbons deposit reformation zone in the sample wells of Minibaevskaya area of Romashkinskoye field. While carrying out this work we examined 11 samples of oil from the Upper Devonian Pashiysky horizon. Four oil samples were collected from wells reckoned among the "anomalous" zones that were marked out according to the results of geophysical, oil field and geological research. Geochemical studies of oils were conducted in the laboratory of geochemistry of the Kazan (Volga-region) Federal University. The wells where the signs of hydrocarbons influx from the deep zones of the crust were recorded are considered to be "anomalous". A number of scientists connect this fact to the hypothesis about periodic influx of deep hydrocarbons to the oil deposits of Romashkinskoye field. Other researchers believe that the source rocks of the adjacent valleys sedimentary cover generate gases when entering the main zone of gas formation, which then migrate up the section and passing through the previously formed deposits of oil, change and "lighten" their composition. Regardless of the point of view on the source of the hydrocarbons, the study of the process of deposits refilling with light hydrocarbons is an

  16. Evidence for the Formation of an Enamine Species during Aldol and Michael-type Addition Reactions Promiscuously Catalyzed by 4-Oxalocrotonate Tautomerase

    NARCIS (Netherlands)

    Poddar, Harshwardhan; Rahimi, Mehran; Geertsema, Edzard; Thunnissen, Andy; Poelarends, Gerrit

    2015-01-01

    The enzyme 4-oxalocrotonate tautomerase (4-OT), which has a catalytic N-terminal proline residue (Pro1), can promiscuously catalyze various carbon–carbon bond-forming reactions, including aldol condensation of acetaldehyde with benzaldehyde to yield cinnamaldehyde, and Michael-type addition of aceta

  17. In-Situ Ligand Formation-Driven Preparation of a Heterometallic Metal-Organic Framework for Highly Selective Separation of Light Hydrocarbons and Efficient Mercury Adsorption.

    Science.gov (United States)

    Han, Yi; Zheng, Hao; Liu, Kang; Wang, Hongli; Huang, Hongliang; Xie, Lin-Hua; Wang, Lei; Li, Jian-Rong

    2016-09-01

    By means of the in situ ligand formation strategy and hard-soft acid-base (HSAB) theory, two types of independent In(COO)4 and Cu6S6 clusters were rationally embedded into the heterometallic metal-organic framework (HMOF) {[(CH3)2NH2]InCu4L4·xS}n (BUT-52). BUT-52 exhibits a three-dimensional (3D) anionic framework structure and has sulfur decorating the dumbbell-shaped cages with the external edges of 24 and 14 Å by the internal edges. Remarkably, because of the stronger charge-induced interactions between the charged MOF skeleton and the easily polarized C2 hydrocarbons (C2s), BUT-52 was used for C2s over CH4 and shows both high adsorption heats of C2s and selective separation abilities for C2s/CH4. Furthermore, BUT-52 also displays efficient mercury adsorption resulting from the stronger-binding ability beween the sulfur and the mercury and can remove 92% mercury from methanol solution even with the initial concentration as low as 100 mg/L. The results in this work indicate the feasibility of BUT-52 for the separation of light hydrocarbons and efficient adsorption/removal of mercury. PMID:27548083

  18. Studies of film formation and erosion by hydrocarbon injection at the plasma edge of TJ-II

    International Nuclear Information System (INIS)

    Injection of methane and ethylene at the plasma edge of the TJ-II stellarator has been performed by using an instrumented, mobile limiter. The insertion of the limiter into the plasma leads to enhanced carbon contamination due to the local deposition of hydrocarbon films. The deposition characteristics of these films, their removal by plasma erosion and the spectroscopic signatures of such erosion have been recorded. The relative erosion efficiency by locally injected hydrogen and plasma particles has been compared. The relative yields of photon emission during the deposition (CH, Hα) and erosion (CH) for the different species used is analysed and compared to pure H injection. It is found that ethylene yields only a 15% of Hα photons per injected molecular H atom compared to H2 fuelling. Also, the ratio of CH/Hα photons delivered upon molecular cracking at the edge is a factor of three higher for ethylene than for methane

  19. Effects of Molecular Structure of the Oxidation Products of Reactive Atmospheric Hydrocarbons on the Formation of Secondary Organic Particular Matter, Including the Effects of Water

    Science.gov (United States)

    Niakan, Negar

    Organic aerosols have significant effects on human health, air quality and climate. Secondary organic aerosols (SOA) are produced by the oxidation of primary-volatile organic compounds (VOC). For example, α-pinene reacts with oxidants such as hydroxyl radical (OH), ozone (O3), and nitrate radical (NO3), accounting for a significant portion of total organic aerosol in the atmosphere. Experimental studies have shown that the oxidation process between α-pinene and ozone has the most significant impact in the formation of SOA (Hoffmann et al., 1997). Most of the models used to predict SOA formation, however, are limited in that they neglect the role of water due to uncertainty about the structure and nature of organic compounds, in addition to uncertainty about the effect of varying relative humidity (RH) on atmospheric organic particulate matter (OPM) (Kanakidou et al., 2005). For this study, structures of organic compounds involved in the formation of SOA are estimated, and the role of water uptake is incorporated in the process. The Combinatorial Aerosol Formation Model (CAFM) is a deterministic model used to determine the amount of organic mass (M o µg m-3) formation based on the predicted structures. Results show that the amount of SOA that is formed is almost negligible when the amount of parent hydrocarbon involved in the reaction is low ( i.e. around 5 µg m-3), especially at lower RH. Observing compounds with a greater number of polar groups (alcohol and carboxylic acid) indicates that structure has a significant effect on organic mass formation. This observation is in agreement with the fact that the more hydrophilic the compound is, the higher RH, leading to more condensation into the PM phase.

  20. Palladium(ii)-catalyzed C-C and C-O bond formation for the synthesis of C1-benzoyl isoquinolines from isoquinoline N-oxides and nitroalkenes.

    Science.gov (United States)

    Li, Jiu-Ling; Li, Wei-Ze; Wang, Ying-Chun; Ren, Qiu; Wang, Heng-Shan; Pan, Ying-Ming

    2016-08-01

    C1-Benzoyl isoquinolines can be generated via a palladium(ii)-catalyzed C-C and C-O coupling of isoquinoline N-oxides with aromatic nitroalkenes. The reaction proceeds through remote C-H bond activation and subsequent intramolecular oxygen atom transfer (OAT). In this reaction, the N-O bond was designed as a directing group in the C-H bond activation as well as the source of an oxygen atom. PMID:27443150

  1. Inhibition of aryl hydrocarbon receptor transactivation and DNA adduct formation by CYP1 isoform-selective metabolic deactivation of benzo[a]pyrene

    International Nuclear Information System (INIS)

    Benzo[a]pyrene (BaP), a polyaromatic hydrocarbon produced by the combustion of cigarettes and coke ovens, is a known procarcinogen. BaP activates the aryl hydrocarbon receptor (AhR) and induces the expression of a battery of genes, including CYP1A1, which metabolize BaP to toxic compounds. The possible role of CYP1 enzymes in mediating BaP detoxification or metabolic activation remains to be elucidated. In this study, we assessed the effects of CYP1 enzymes (CYP1A1, CYP1A2 and CYP1B1) on BaP-induced AhR transactivation and DNA adduct formation in HEK293 cells and HepG2 cells. Transfection of CYP1A1 and CYP1B1, but not CYP1A2, suppressed BaP-induced activation of AhR. Expression of CYP1A1 and CYP1A2, but not CYP1B1, inhibited DNA adduct formation in BaP-treated HepG2 cells. These results indicate that CYP1A1 and CYP1B1 play a role in deactivation of BaP on AhR and that CYP1A1 and CYP1A2 are involved in BaP detoxification by suppressing DNA adduct formation. BaP treatment did not induce DNA adduct formation in HEK293 cells, even after transfection of CYP1 enzymes, suggesting that expression of CYP1 enzymes is not sufficient for DNA adduct formation. Lower expression of epoxide hydrolase and higher expression of glutathione S-transferase P1 (GSTP1) and GSTM1/M2 were observed in HEK293 cells compared with HepG2 cells. Dynamic expression of CYP1A1, CYP1A2 and CYP1B1 along with expression of other enzymes such as epoxide hydrolase and phase II enzymes may determine the detoxification or metabolic activation of BaP

  2. A 4D synchrotron X-ray tomography study of the formation of hydrocarbon migration pathways in heated organic-rich shale

    OpenAIRE

    Panahi, Hamed; Kobchenko, Maya; RENARD, Francois; Mazzini, Adriano; Scheibert, Julien; Dysthe, Dag Kristian; Jamtveit, Bjorn; Malthe-Sørenssen, Anders; Meakin, Paul

    2013-01-01

    Recovery of oil from oil shales and the natural primary migration of hydrocarbons are closely related processes that have received renewed interests in recent years because of the ever tightening supply of conventional hydrocarbons and the growing production of hydrocarbons from low permeability tight rocks. Quantitative models for conversion of kerogen into oil and gas and the timing of hydrocarbon generation have been well documented. However, lack of consensus about the kinetics of hydroca...

  3. LIPASE-CATALYZED TRANSESTERIFICATION OF PALM KERNEL OIL WITH DIALKYLCARBONATES

    Directory of Open Access Journals (Sweden)

    Tjahjono Herawan

    2014-01-01

    Full Text Available Lipase-catalyzed transesterifications-especially in a solvent-free medium-are important for industrial applications because such systems would have an enormous advantage by avoiding the problem of separation, toxicity and flammability of organic solvents. However, the organic solvent-free alcoholysis, especially methanolysis, does not give high conversions. The same problem also occurs when ethyl or methyl acetate are used as acyl acceptors. The main problems of lipase-catalyzed organic solvent-free alcoholysis are first, the solubility of the plant oil in the substrate or solvent and second, the fact that transesterification is an equilibrium reaction. Dialkyl carbonates, versatile compounds due to their chemical reactivity and physical properties, may provide an alternative to solve both problems. Using dialkyl carbonates transesterification is not an equilibrium reaction, because the intermediate compound immediately decomposes to carbon dioxide and an alcohol. Moreover, dialkyl carbonates (especially dimethyl carbonate are cheap and widely available. For single step lipase-catalyzed transesterification of palm kernel oil, diakyl carbonates (in this case dimethyl and diethyl carbonate gave better yields compared to those of short chain alcohols. The rate of ester formation with dialkyl carbonates as substrate was about 6-7 times higher than that obtained with short chain alcohols. The formation of esters was gradually increased by a higher enzyme amount from 5-20% (w/w of oil for 8 h reaction time. However from the economic point of view, an enzyme amount of 10% on the weight base of oil was proposed for further reaction. Generally, the highest ester formation was observed when a temperature of 60°C was used. However, in the case of dimethyl carbonate little difference was observed at reaction temperatures of 60 and 70oC and the reactions proceeded nearly identically. The esters formation increased drastically up to more than 70% when water

  4. Parameters affecting incorporation and by-product formation during the production of structured phospholipids by lipase-catalyzed acidolysis in solvent free system

    DEFF Research Database (Denmark)

    Vikbjerg, Anders Falk; Mu, Huiling; Xu, Xuebing

    2005-01-01

    minimize by-products during reaction. In the present study we examined the Lipozyme RM IM-catalyzed acidolysis for the production of structured phospholipids between phosphatidylcholine (PC) and caprylic acid in the solvent free system. A five-factor response surface design was used to evaluate the...... opposite effect. The PC content decreased with increase of all parameters except for substrate ratio. Optimal conditions are recommended as enzyme dosage 40%, reaction temperature 55°C, water addition 1%, reaction time 70h, and substrate ratio 6 mol/mol caprylic acid/PC. Under these conditions an...

  5. Modeling the formation, decay, and partitioning of semivolatile nitro-polycyclic aromatic hydrocarbons (nitronaphthalenes) in the atmosphere

    DEFF Research Database (Denmark)

    Feilberg, A.; Kamens, R.M.; Strommen, M.R.;

    1999-01-01

    these types of mechanisms can be used to model nitronaphthalene formation and decay in regional airmasses. The partitioning experiments were conducted at night. The sampling system consisted of two Teflon impregnated glass fiber filters followed by a gas-phase denuder. Evidence is provided that...

  6. Early diagenetic growth of carbonate concretions in the upper Doushantuo Formation in South China and their significance for the assessment of hydrocarbon source rock

    Institute of Scientific and Technical Information of China (English)

    DONG Jin; ZHANG ShiHong; JIANG GanQing; ZHAO QingLe; LI HaiYan; SHI XiaoYing; LIU JunLai

    2008-01-01

    Mineralogical and textural characteristics and organic carbon composition of the carbonate concretions from the upper Doushantuo Formation (ca.551 Ma) in the eastern Yangtze Gorge area reveal their early diagenetic (shallow) growth in organic-rich shale.High organic carbon content (up to 10%) and abundance of framboidal pyrites in the hosting shale suggest an anoxic or euxinic depositional environment.Well-preserved cardhouse clay fabrics in the concretions suggest their formation at 0-3 m burial depth, likely associated with microbial decomposition of organic matter and anaerobic oxidation of methane.Gases through decomposition of organic matter and/or from methanogenesis created bubbles and cavities, and anaerobic methane oxidation at the sulfate reduction zone resulted in carbonate precipitation, filling in bubbles and cavities to form spherical structures of the concretions.Rock pyrolysis analyses show that the carbonate concretions have lower total organic carbon (TOC) content but higher effective carbon than those in the host rocks.This may be caused by enclosed organic matter in pores of the concretions so that organic matter was protected from further modification during deep burial and maintained high hydrocarbon generating potential even in over-matured source rock.As a microbialite sensu latu, concretions have special growth conditions and may provide important information on the microbial activities in depositional and early burial environments.

  7. Early diagenetic growth of carbonate concretions in the upper Doushantuo Formation in South China and their significance for the assessment of hydrocarbon source rock

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Mineralogical and textural characteristics and organic carbon composition of the carbonate concretions from the upper Doushantuo Formation (ca. 551 Ma) in the eastern Yangtze Gorge area reveal their early diagenetic (shallow) growth in organic-rich shale. High organic carbon content (up to 10%) and abundance of framboidal pyrites in the hosting shale suggest an anoxic or euxinic depositional environment. Well-preserved cardhouse clay fabrics in the concretions suggest their formation at 0-3 m burial depth, likely associated with microbial decomposition of organic matter and anaerobic oxidation of methane. Gases through decomposition of organic matter and/or from methanogenesis created bubbles and cavities, and anaerobic methane oxidation at the sulfate reduction zone resulted in carbonate precipitation, filling in bubbles and cavities to form spherical structures of the concretions. Rock pyrolysis analyses show that the carbonate concretions have lower total organic carbon (TOC) content but higher effective carbon than those in the host rocks. This may be caused by enclosed organic matter in pores of the concretions so that organic matter was protected from further modification during deep burial and maintained high hydrocarbon generating potential even in over-matured source rock. As a microbialite sensu latu, concretions have special growth conditions and may provide important information on the microbial activities in depositional and early burial environments.

  8. Effect of SO2 concentration on SOA formation in a photorreactor from a mixture of anthropogenic hydrocarbons and HONO

    Science.gov (United States)

    García Vivanco, Marta; Santiago, Manuel; García Diego, Cristina; Borrás, Esther; Ródenas, Milagros; Martínez-Tarifa, Adela

    2010-05-01

    Sulfur dioxide (SO2) is an important urban atmospheric pollutant, mainly produced by the combustion of fossil fuels containing sulfur. In the atmosphere, SO2 can react with OH radicals to form sulfuric acid, which can condense to form acidic aerosol. Sulfuric acid particles act as an acid catalyst for some heterogeneous carbonyl reactions like hydration, polymerization or acetals formation, which may lead to a large increase on SOA mass. In order to evaluate the effect of the SO2 concentration on SOA formation, 3 experiments were performed during the campaign carried out by CIEMAT on the EUPHORE facility (CEAM, Valencia, Spain) during June- July 2008. The objective of the campaign was to evaluate the effect of different experimental conditions on SOA formation from the photooxidation of some anthropogenic and biogenic VOCs using HONO as oxidant. Experiment on 6/17/08 was selected as base case (no SO2 was introduced) and experiments 6/26/08 and 7/1/08 were selected as high SO2 (2600 ug/m3) and low SO2 (60 ug/m3) concentration experiments respectively. In the three experiments a mixture of toluene, 1,3,5-TMB (trimethylbenzene), o-xylene and octane was selected as the parent VOCs. Single and coupled to mass spectroscopy gas cromatography (GC and GC/MS), as well as high performance liquid chromatography (HPLC) and Fourier transform infrared spectroscopy (FTIR) were used to measure the initial VOCs and oxidant concentrations decay and the formation of gas phase oxidation products through the experiments. Aerosol size distribution and concentration were measured with SMPS (scanning mobility particle sizer) and TEOM (tapered element oscillating monitor) respectively. In addition, analysis of the organic and inorganic aerosol content was also performed via filter sampling followed by GC/MS and ionic chromatography (for organic and inrganic content respectively). Comparing the filters collected in the three experiments, clearly the largest mass aerosol formation is observed

  9. Effect of hydrocarbons and nitrogen oxides on ozone formation in smog chambers exposed to solar irradiance of Mexico City

    Energy Technology Data Exchange (ETDEWEB)

    Sandoval F, J; Marroquin de la R, O; Jaimes L, J. L; Zuniga L, V. A; Gonzalez O, E; Guzman Lopez-Figueroa, F [Instituto Mexicano del Petroleo, Mexico, D.F. (Mexico)

    2001-01-01

    Outdoor smog chambers experiments were performed on air to determine the answer of maximum ozone levels, to changes in the initial hydrocarbons, HC, and nitrogen oxide NO{sub x}. These captive-air experiments under natural irradiation were carried out. Typically, eight chambers were filled with Mexico city air in the morning. In some of those chambers, the initial HC and/or Nox concentrations were varied by {+-}25% to {+-}50% by adding various combinations of a mixture of HC, clean air, or NO{sub x} (perturbed chambers). The O{sub 3} and NO{sub x} concentration in each chamber was monitored throughout the day to determine O{sub 3} (max). The initial HC and NO{sub x} concentration effects were determined by comparing the maximum ozone concentrations measured in the perturbed and unperturbed chambers. Ozone isopleths were constructed from the empirical model obtained of measurements of the eight chambers and plotted in a graph whose axe were the initial HC and NO{sub x} values. For the average initial conditions that were measured in Mexico City, it was found that the most efficient strategy to reduce the maximum concentration of O{sub 3} is the one that reduces NO{sub x}. [Spanish] Se realizaron experimentos de camaras de esmog con el aire de la ciudad de Mexico para determinar las respuestas de los niveles maximos de ozono a los cambios en las concentraciones iniciales de hidrocarburos, HC y oxido de nitrogeno, NO{sub x}. Por lo general, se llenaron 8 bolsas con aire matutino de la Ciudad de Mexico. En algunas camaras, las concentraciones iniciales fueron cambiadas de 25% a 50%, anadiendo varias concentraciones de una mezcla de HC, aire limpio y/o NO{sub x}. La concentracion de O{sub 3} y NO{sub x}, en cada camara, fueron monitoreadas a lo largo del dia para determinar el maximo de O{sub 3}. El efecto de los HC y el NO{sub x} fue determinado por comparacion del maximo de ozono formado en las camaras, que fueron perturbadas por adicion o reduccion de HC y/o Nox

  10. Colorimetric and visual detection of tyrosine based on its copper-catalyzed enzymatic oxidation to dopamine and subsequent reductive formation of colored gold nanoparticles using copper ions

    International Nuclear Information System (INIS)

    We describe a highly sensitive and selective colorimetric test for L-tyrosine (Tyr). It is based on the tyrosinase-catalyzed oxidation of Tyr to dopamine, and its subsequent reaction with tetrachloroaurate to form gold particles whose purple color can be detected even with bare eyes. We also show that the enzymatic oxidation of Tyr proceeds faster in the presence of Cu(II) ions. A 2:1 ratio of Tyr to Cu(II) was found to give the best results. Tryptophan and threonine do no interfere in this assay. The spectrophotometric detection limit for Tyr is 8 × 10−7 mol L−1. Compared to others, this assay is simple, rapid, and label-free but yet enables visual read-out. (author)

  11. Coke Formation During Hydrocarbons Pyrolysis. Part One: Steam Cracking Formation de coke pendant la pyrolise des hydrocarbures. Première partie : vapocraquage

    Directory of Open Access Journals (Sweden)

    Weill J.

    2006-11-01

    Full Text Available Thermal cracking is always accompanied by coke formation, which becomes deposited on the wall and limits heat transfers in the reactor while increasing pressure drops and possibly even plugging up the reactor. This review article covers undesirable coking operations in steam craking reactors. These coking reactions may take place in the gas phase and/or on the surface of the reactor, with coke being produced during pyrolysis by a complex mechanism that breaks down into a catalytic sequence and a noncatalytic sequence. After a brief description of different experimental set-ups used to measure the coke deposition, on the basis of research described in the literature, the different factors and their importance for coke formation are listed. In particular, we describe the effects of surface properties of stainless-steel and quartz reactors as well as the influence of the cracked feedstock, of temperature, of dilution, of residence time and of the conversion on coke deposition. Some findings about the morphology of coke are described and linked to formation mechanisms. To illustrate this review, some particularly interesting research is referred to concerning models developed to assess coke formation during propane steam cracking. Le craquage thermique est toujours accompagné de la formation de coke qui, en se déposant à la paroi, limite les transferts de chaleur au réacteur, augmente les pertes de charges et même peut boucher celui-ci. Cet article fait le point sur les réactions indésirables de cokage dans les réacteurs de vapocraquage. Ces réactions de cokage peuvent avoir lieu en phase gazeuse et/ou sur la surface du réacteur, le coke étant produit pendant la pyrolyse par un mécanisme complexe qui se décompose en une séquence catalytique et une séquence non catalytique. Après une brève présentation des différents montages expérimentaux utilisés pour mesurer le dépôt de coke, il est mentionné, à partir de travaux de la

  12. Coke Formation During Hydrocarbons Pyrolysis. Part One: Steam Cracking Formation de coke pendant la pyrolise des hydrocarbures. Première partie : vapocraquage

    OpenAIRE

    Weill J.; Broutin P.; Billaud F.; Gueret C.

    2006-01-01

    Thermal cracking is always accompanied by coke formation, which becomes deposited on the wall and limits heat transfers in the reactor while increasing pressure drops and possibly even plugging up the reactor. This review article covers undesirable coking operations in steam craking reactors. These coking reactions may take place in the gas phase and/or on the surface of the reactor, with coke being produced during pyrolysis by a complex mechanism that breaks down into a catalytic sequence an...

  13. The coupling formation process of four centers of hydrocarbon in Sinian Dengying Formation of Sichuan Basin%四川盆地震旦系灯影组油气四中心耦合成藏过程

    Institute of Scientific and Technical Information of China (English)

    刘树根; 秦川; 孙玮; 王国芝; 徐国盛; 袁海锋; 张长俊; 张志敬

    2012-01-01

    四川盆地元古界震旦系灯影组,时代老、埋藏深,天然气藏形成经历了生气中心(古油藏和未成藏石油的富集区)-储气中心(古气藏和未成藏天然气及水溶气的富集区)-保气中心(现今气藏和未成藏天然气及水溶气的富集区)的变换过程.生气中心是储气中心的主要“气源”、储气中心是现今保气中心的主要“气源”.生气中心的形成受控于烃源岩所在部位的生烃中心(烃源灶).震旦系灯影组天然气藏的形成是在多期构造作用控制下由油气的四中心(生烃中心、生气中心、储气中心和保气中心)的耦合关系决定的.油气能否成藏和保存下来的关键取决于烃源是否丰富和保存条件是否较佳,即具有源盖联合控烃控藏的特征.生烃中心受控于盆地的原型格局,形成后其空间位置即无变动性;而其余三中心受构造作用的控制而变动性较易和较大.因此,“三中心”(生气中心、储气中心和保气中心)在空间上的分布关系,决定了油气的最终分布.威远-资阳震旦系灯影组气田的成藏过程是典型的储气中心和保气中心短距离(30km)移位的耦合关系;川东南丁山-林滩场震旦系灯影组古油气藏的形成及破坏过程是典型的缺乏保气中心的耦合关系.%Dengying Formation of Late Sinian age located in the Sichuan Basin was deeply buried and its paleo-oil pool (gas generating center) was transformed into paleo-gas pool (gas accumulating center) and present gas pool (gas preserving center). Paleo-oil pool was the main "hydrocarbon source" for the paleo-gas pool which was also the main "hydrocarbon source" of present gas pooL The formation of paleo-oil pool was controlled by the occurrence and location of source rocks ( hydrocarbon generating center) . Therefore the formation of present natural gas pool in the Upper Sinian Dengying Formation was determined by the coupling process of hydrocarbon generating

  14. Influence of oil and gas field operations on spatial and temporal distributions of atmospheric non-methane hydrocarbons and their effect on ozone formation in winter

    Directory of Open Access Journals (Sweden)

    R. A. Field

    2014-09-01

    Full Text Available Emissions from oil and natural gas development during winter in the Upper Green River Basin of Wyoming are known to drive episodic ozone (O3 production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes in 2011 compared to none in 2012. During 2011 wintertime O3 episodes at two sites near Boulder Wyoming, situated ∼5 km apart, were observed to sometimes differ. In 2012 the lack of O3 episodes coincided with a reduction in ambient levels of total non-methane hydrocarbons (NMHC. Measurements of speciated NMHC, and other air quality parameters, were performed to better understand emission sources and to determine which compounds are most active in promoting O3 formation. Positive Matrix Factorization (PMF analyses of the data were carried out to help achieve these goals. PMF analyses revealed three contributing factors that were identified with different emission source types: factor 1, combustion/traffic; factor 2, fugitive natural gas; and factor 3, fugitive condensate. Compositional signatures of three contributing factors were identified through comparison with independently derived emission source profiles. Fugitive emissions of natural gas and of condensate were the two principal emission source types for NMHC. A water treatment and recycling facility was found to be a significant source of condensate range NMHC, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

  15. Microbial formation and degradation of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in soil during short-term incubation

    International Nuclear Information System (INIS)

    We tested whether OPAHs were formed during 19-wk incubation of a fertile soil at optimum moisture in the dark. The soil had initial mean (±s.e., n = 3) concentrations of 22 ± 1.7 (Σ28PAHs) and 4.2 ± 0.34 μg g−1 (Σ14OPAHs). After 19 wk, individual PAH and OPAH concentrations had decreased by up to 14 and 37%, respectively. Decreases in % of initial concentrations were positively correlated with their KOW values for PAHs (r = 0.48, p = 0.022) and 9 OPAHs (r = 0.78, p = 0.013) but negatively, albeit not significantly, for 5 OPAHs (r = −0.75, p = 0.145) suggesting net formation of some OPAHs. The latter was supported by significantly increasing 1-indanone/fluorene ratios while the other OPAH to parent-PAH ratios remained constant or tended to increase. We conclude that OPAHs are formed in soils during microbial turnover of PAHs in a short time. -- Highlights: • Some OPAHs were microbially produced in an urban soil with aged PAHs contamination. • Naphthalene and acenaphthylene were microbially produced in a fertile urban soil. • KOW values predicted degradation of PAHs and those OPAHs which were not net formed. • OPAH concentrations must be controlled during remediation of PAH-contaminated soil. -- In soil, low molecular weight PAHs and some OPAHs are formed microbially during incubation of four months

  16. Approach to Recover Hydrocarbons from Currently Off-Limit Areas of the Antrim Formation, MI Using Low-Impact Technologies

    Energy Technology Data Exchange (ETDEWEB)

    James Wood; William Quinlan

    2008-09-30

    The goal of this project was to develop and execute a novel drilling and completion program in the Antrim Shale near the western shoreline of Northern Michigan. The target was the gas in the Lower Antrim Formation (Upper Devonian). Another goal was to see if drilling permits could be obtained from the Michigan DNR that would allow exploitation of reserves currently off-limits to exploration. This project met both of these goals: the DNR (Michigan Department of Natural Resources) issued permits that allow drilling the shallow subsurface for exploration and production. This project obtained drilling permits for the original demonstration well AG-A-MING 4-12 HD (API: 21-009-58153-0000) and AG-A-MING 4-12 HD1 (API: 21-009-58153-0100) as well as for similar Antrim wells in Benzie County, MI, the Colfax 3-28 HD and nearby Colfax 2-28 HD which were substituted for the AG-A-MING well. This project also developed successful techniques and strategies for producing the shallow gas. In addition to the project demonstration well over 20 wells have been drilled to date into the shallow Antrim as a result of this project's findings. Further, fracture stimulation has proven to be a vital step in improving the deliverability of wells to deem them commercial. Our initial plan was very simple; the 'J-well' design. We proposed to drill a vertical or slant well 30.48 meters (100 feet) below the glacial drift, set required casing, then angle back up to tap the resource lying between the base to the drift and the conventional vertical well. The 'J'-well design was tested at Mancelona Township in Antrim County in February of 2007 with the St. Mancelona 2-12 HD 3.

  17. Levan fructotransferase from Arthrobacter oxydans J17-21 catalyzes the formation of the di-D-fructose dianhydride IV from levan.

    Science.gov (United States)

    Jang, Ki-Hyo; Ryu, Eun-Ja; Park, Buem-Seek; Song, Ki-Bang; Kang, Soon Ah; Kim, Chul Ho; Uhm, Tai-Boong; Park, Yong-Il; Rhee, Sang-Ki

    2003-04-23

    A new levan fructotransferase (LFTase) isolated from Arthrobacter oxydans J17-21 was characterized for the production of difructose dianhydride IV (DFA IV). LFTase was purified to apparent homogeneity by Q-Sepharose ion exchange chromatography, Mono-Q HR 5/5 column chromatography, and gel permeation chromatography. The enzyme had an apparent molecular mass of 54000 Da. The optimum pH for the enzyme-catalyzed reaction was pH 6.5, and the optimum temperature was observed at 45 degrees C. The LFTase was activated by the presence of CaCl(2) and EDTA-2Na but inhibited strongly by MnCl(2) and CuSO(4) at 1 mM and completely by FeSO(4) and Ag(2)SO(4) at 1 mM. A bacterial levan from Zymomonas mobilis was incubated with an LFTase; final conversion yield from the levan to DFA IV was 35%. Neither inulin, levanbiose, sucrose, dextran, nor starch was hydrolyzed by LFTase. DFA IV was very stable at acidic pH and high temperature, thus indicating that DFA IV may be suitable for the food industry and related areas. PMID:12696949

  18. The effects of cooking on wire and stone barbecue at different cooking levels on the formation of heterocyclic aromatic amines and polycyclic aromatic hydrocarbons in beef steak.

    Science.gov (United States)

    Oz, Fatih; Yuzer, M Onur

    2016-07-15

    The effects of type of barbecue (wire and stone) and cooking levels (rare, medium, well-done and very well-done) on the formation of heterocyclic aromatic amines (HCAs) and polycyclic aromatic hydrocarbons (PAHs) in beef steak were investigated. Varying levels of IQx (up to 0.29ng/g), IQ (up to 0.93ng/g), MeIQx (up to 0.08ng/g), MeIQ (up to 0.75ng/g), 7,8-DiMeIQx (up to 0.08ng/g), 4,8-DiMeIQx (up to 4.95ng/g), PhIP (up to 6.24ng/g) and AαC (up to 0.20ng/g) were determined, while MeAαC was not detected. The total HCA amounts in wire barbecued samples were higher than stone barbecued samples. Total HCA contents of the samples ranged between nd and 13.52ng/g. In terms of PAHs, varying levels of BaA (up to 0.34ng/g), Chry (up to 0.28ng/g), BbF (up to 0.39ng/g), BkF (up to 0.90ng/g), BaP (up to 0.29ng/g) and Bghip (up to 0.43ng/g) were determined, while DahA and IncdP were not detected. The total PAH amounts in stone barbecued samples were higher than those of wire barbecued samples. Total PAH amounts of the samples ranged between nd and 2.63ng/g. PMID:26948589

  19. Method for producing viscous hydrocarbons

    Science.gov (United States)

    Poston, Robert S.

    1982-01-01

    A method for recovering viscous hydrocarbons and synthetic fuels from a subterranean formation by drilling a well bore through the formation and completing the well by cementing a casing means in the upper part of the pay zone. The well is completed as an open hole completion and a superheated thermal vapor stream comprised of steam and combustion gases is injected into the lower part of the pay zone. The combustion gases migrate to the top of the pay zone and form a gas cap which provides formation pressure to produce the viscous hydrocarbons and synthetic fuels.

  20. Muon Catalyzed Fusion

    Science.gov (United States)

    Armour, Edward A.G.

    2007-01-01

    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  1. Apparatus for hydrocarbon extraction

    Science.gov (United States)

    Bohnert, George W.; Verhulst, Galen G.

    2013-03-19

    Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

  2. 4-Dimenthylaminopyridine or Acid-Catalyzed Synthesis of Esters: A Comparison

    Science.gov (United States)

    van den Berg, Annemieke W. C.; Hanefeld, Ulf

    2006-01-01

    A set of highly atom-economic experiments was developed to highlight the differences between acid- and base-catalyzed ester syntheses and to introduce the principles of atom economy. The hydrochloric acid-catalyzed formation of an ester was compared with the 4-dimethylaminopyradine-catalyzed ester synthesis.

  3. On electron trapping in crystalline hydrocarbon matrices

    International Nuclear Information System (INIS)

    The formation of trapped electrons in γ irradiated polycrystalline hydrocarbon matrices is examined by E.S.R. at 77 and 4 K. Results indicate that no thermalized electrons are trapped in polycrystalline matrices of linear hydrocarbons (from n-hexane to n-hexadecane). They also strongly suggest that the trapped electrons in polycrystalline hydrocarbons so far reported may have been trapped in glassy regions in the matrices used. (author)

  4. Coke Formation During Hydrocarbons Pyrolysis. Part Two: Methane Thermal Cracking Formation de coke pendant la pyrolyse des hydrocarbures. Deuxième partie : pyrolyse du méthane

    Directory of Open Access Journals (Sweden)

    Billaud F.

    2006-11-01

    Full Text Available Part one of this article dealt with coking in a steam cracking furnace. In this process, coke deposition is a very complex phenomenon due to the number of parameters involved. Nevertheless, for this process, coke deposition is a secondary reaction which does not affect steam cracking yields. It is completely different for methane thermal cracking. Coke is one of the main products of this reaction. Part two of this article deals with coke deposition on the walls of the reactors used for methane thermal cracking. After a brief description of the different set-ups used to study coke deposition, the main parameters involved are listed. The importance of temperature, conversion, type of diluent, and hydrocarbon partial pressure will be enhanced. To conclude, two approaches to the mechanism are proposed to explain coke formation during methane thermal cracking. La première partie de cet article faisait le point sur les réactions indésirables de cokage dans les réacteurs de vapocraquage : dans le cadre de ce procédé, la formation de coke est un phénomène complexe du fait du nombre important de paramètres mis en jeu. Toutefois, pour ce procédé, la réaction de formation du coke à la paroi des réacteurs est une réaction secondaire qui n'affecte pas les rendements de vapocraquage. Ceci est complètement différent dans le cas de la pyrolyse thermique du méthane, procédé pour lequel le coke est un produit principal et indésirable de la réaction. La seconde partie de cet article est consacrée plus particulièrement à la formation du coke, lors de la pyrolyse du méthane et présente les principaux résultats expérimentaux décrits dans la littérature. Parmi les différents montages expérimentaux utilisés pour mesurer le dépôt de coke, il est mentionné, à partir des travaux de la littérature, les 2 techniques suivantes : - la technique de la paroi chaude, - la technique du fil chaud. Pour la première technique, les montages exp

  5. Heterogeneous reactions between ions NH3+and NH+andhydrocarbons adsorbed on a tungsten surface.Formation of HCN+in NH+-surface hydrocarbon collisions

    Czech Academy of Sciences Publication Activity Database

    Harnisch, M.; Scheier, P.; Herman, Zdeněk

    2015-01-01

    Roč. 392, DEC 2015 (2015), s. 139-144. ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : ion-surface collisions * NH3+and NH+projectiles * surface hydrocarbons Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.972, year: 2014

  6. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    International Nuclear Information System (INIS)

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed

  7. Chemical and mechanical properties of silica hybrid films from NaOH catalyzed sols for micromachining with diamond cutting tools

    Energy Technology Data Exchange (ETDEWEB)

    Prenzel, T., E-mail: tprenzel@uni-bremen.de [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Mehner, A. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Lucca, D.A.; Qi, Y.; Harriman, T.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Mutlugünes, Y. [Labor für Mikrozerspanung — LFM, Badgasteiner Str. 2, 28359 Bremen (Germany); Shojaee, S.A. [School of Mechanical and Aerospace Engineering, 218 Engineering North, Oklahoma State University, Stillwater, OK 74078 (United States); Wang, Y.Q.; Williams, D. [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Nastasi, M. [Nebraska Center for Energy Sciences Research, University of Nebraska, 230 Whittier Research Center, 2200 Vine Street Lincoln, NE 68583-0857 (United States); Zoch, H.-W. [Stiftung Institut für Werkstofftechnik, Badgasteiner Str. 3, 28359 Bremen (Germany); Swiderek, P. [Institute of Applied and Physical Chemistry, University of Bremen, Leobener Straße, 28359 Bremen (Germany)

    2013-03-01

    Manufacturing of microstructured mold surfaces was realized by the micromachining of thick sol–gel silica hybrid coatings. The films were deposited onto pre-machined steel molds by spin coating using NaOH-catalyzed sols from organosilicate precursors. The effect of the sol synthesis and the heat treatment on the mechanical and chemical properties of these films was studied in order to develop thick and crack-free films with appropriate properties for micromachining with diamond cutting tools. The hardness was measured by nanoindentation as a function of the heat treatment temperature. The transition from soft organic gel films to hard glass-like films due to the thermal treatment was characterized by X-ray photoelectron spectroscopy, elastic recoil detection, and Raman and infrared spectroscopies. The films from NaOH catalyzed sols showed a complex transition from aliphatic carbon originating from hydrocarbon groups to carbonates, carboxylates and disordered carbon clusters. - Highlights: ► Thick silica hybrid films were micromachined with diamond cutting tools. ► The nanoindentation hardness increased with the heat treatment temperature. ► The role of sodium hydroxide in base catalyzed silica sols was studied. ► Formation of carbonates, carboxylates and disordered carbon was observed.

  8. A propionate CoA-transferase of Ralstonia eutropha H16 with broad substrate specificity catalyzing the CoA thioester formation of various carboxylic acids.

    Science.gov (United States)

    Lindenkamp, Nicole; Schürmann, Marc; Steinbüchel, Alexander

    2013-09-01

    In this study, we have investigated a propionate CoA-transferase (Pct) homologue encoded in the genome of Ralstonia eutropha H16. The corresponding gene has been cloned into the vector pET-19b to yield a histidine-tagged enzyme which was expressed in Escherichia coli BL21 (DE3). After purification, high-performance liquid chromatography/mass spectrometry (HPLC/MS) analyses revealed that the enzyme exhibits a broad substrate specificity for carboxylic acids. The formation of the corresponding CoA-thioesters of acetate using propionyl-CoA as CoA donor, and of propionate, butyrate, 3-hydroxybutyrate, 3-hydroxypropionate, crotonate, acrylate, lactate, succinate and 4-hydroxybutyrate using acetyl-CoA as CoA donor could be shown. According to the substrate specificity, the enzyme can be allocated in the family I of CoA-transferases. The apparent molecular masses as determined by gel filtration and detected by SDS polyacrylamide gel electrophoresis were 228 and 64 kDa, respectively, and point to a quaternary structure of the native enzyme (α4). The enzyme exhibited similarities in sequence and structure to the well investigated Pct of Clostridium propionicum. It does not contain the typical conserved (S)ENG motif, but the derived motif sequence EXG with glutamate 342 to be, most likely, the catalytic residue. Due to the homo-oligomeric structure and the sequence differences with the subclasses IA-C of family I CoA-transferases, a fourth subclass of family I is proposed, comprising - amongst others - the Pcts of R. eutropha H16 and C. propionicum. A markerless precise-deletion mutant R. eutropha H16∆pct was generated. The growth and accumulation behaviour of this mutant on gluconate, gluconate plus 3,3'-dithiodipropionic acid (DTDP), acetate and propionate was investigated but resulted in no observable phenotype. Both, the wild type and the mutant showed the same growth and storage behaviour with these carbon sources. It is probable that R. eutropha H16 is upregulating

  9. Hydrogen evolution catalyzed by cobaloximes.

    Science.gov (United States)

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B

    2009-12-21

    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

  10. Detailed mechanism of the autoxidation of N-hydroxyurea catalyzed by a superoxide dismutase mimic Mn(III) porphyrin: formation of the nitrosylated Mn(II) porphyrin as an intermediate.

    Science.gov (United States)

    Kalmár, József; Biri, Bernadett; Lente, Gábor; Bányai, István; Budimir, Ana; Biruš, Mladen; Batinić-Haberle, Ines; Fábián, István

    2012-10-14

    The in vitro autoxidation of N-hydroxyurea (HU) is catalyzed by Mn(III)TTEG-2-PyP(5+), a synthetic water soluble Mn(III) porphyrin which is also a potent mimic of the enzyme superoxide dismutase. The detailed mechanism of the reaction is deduced from kinetic studies under basic conditions mostly based on data measured at pH = 11.7 but also including some pH-dependent observations in the pH range 9-13. The major intermediates were identified by UV-vis spectroscopy and electrospray ionization mass spectrometry. The reaction starts with a fast axial coordination of HU to the metal center of Mn(III)TTEG-2-PyP(5+), which is followed by a ligand-to-metal electron transfer to get Mn(II)TTEG-2-PyP(4+) and the free radical derived from HU (HU˙). Nitric oxide (NO) and nitroxyl (HNO) are minor intermediates. The major pathway for the formation of the most significant intermediate, the {MnNO} complex of Mn(II)TTEG-2-PyP(4+), is the reaction of Mn(II)TTEG-2-PyP(4+) with NO. We have confirmed that the autoxidation of the intermediates opens alternative reaction channels, and the process finally yields NO(2)(-) and the initial Mn(III)TTEG-2-PyP(5+). The photochemical release of NO from the {MnNO} intermediate was also studied. Kinetic simulations were performed to validate the deduced rate constants. The investigated reaction has medical implications: the accelerated production of NO and HNO from HU may be utilized for therapeutic purposes. PMID:22911446

  11. Hydrocarbon filling history and reservoir continuity of oil fields evaluated using {sup 87}Sr/{sup 86}Sr isotope ratio variations in formation water, with examples from the North Sea

    Energy Technology Data Exchange (ETDEWEB)

    Mearns, E.W.; McBride, J.J. [Isotopic Analytical Services Ltd., Aberdeen (United Kingdom)

    1999-02-01

    This paper describes how {sup 87}Sr/{sup 86}Sr ratios in formation waters are used to evaluate compartmentalisation of hydrocarbon reservoirs. Strontium Isotope Residual Salt Analysis (SrRSA) of core samples provides a means of measuring {sup 87}Sr/{sup 86}Sr ratios in formation water from hydrocarbon columns and aquifers. Smooth SrRSA profiles suggest progressive, uninterrupted, filling and the absence of sealed barriers, while a step change in a profile normally suggests a barrier sealed up-dip from the well penetration. Inferences about lateral connectivity are made by comparing SrRSA profiles from neighbouring wells at TVD. Profiles that are superimposed when plotted at TVD suggest the well sections share a common filling history and lie in the same flow unit. Neighbouring SrRSA profiles that are not superimposed normally suggest segmented compartmentalisation of the reservoir. Post-fill structural tilting of reservoirs and hydrodynamism synchronous with filling are processes which complicate data interpretation. Drilling mud contamination of core water is the most serious technical limitation of the SrRSA technique. (Author)

  12. Tritium catalyzed deuterium tokamaks

    International Nuclear Information System (INIS)

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the 3He from the D(D,n)3He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general)

  13. Coupling Oxygen Consumption with Hydrocarbon Oxidation in Bacterial Multicomponent Monooxygenases.

    Science.gov (United States)

    Wang, Weixue; Liang, Alexandria D; Lippard, Stephen J

    2015-09-15

    A fundamental goal in catalysis is the coupling of multiple reactions to yield a desired product. Enzymes have evolved elegant approaches to address this grand challenge. A salient example is the biological conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily. sMMO is a dynamic protein complex of three components: a hydroxylase, a reductase, and a regulatory protein. The active site, a carboxylate-rich non-heme diiron center, is buried inside the 251 kDa hydroxylase component. The enzyme processes four substrates: O2, protons, electrons, and methane. To couple O2 activation to methane oxidation, timely control of substrate access to the active site is critical. Recent studies of sMMO, as well as its homologues in the BMM superfamily, have begun to unravel the mechanism. The emerging and unifying picture reveals that each substrate gains access to the active site along a specific pathway through the hydroxylase. Electrons and protons are delivered via a three-amino-acid pore located adjacent to the diiron center; O2 migrates via a series of hydrophobic cavities; and hydrocarbon substrates reach the active site through a channel or linked set of cavities. The gating of these pathways mediates entry of each substrate to the diiron active site in a timed sequence and is coordinated by dynamic interactions with the other component proteins. The result is coupling of dioxygen consumption with hydrocarbon oxidation, avoiding unproductive oxidation of the reductant rather than the desired hydrocarbon. To initiate catalysis, the reductase delivers two electrons to the diiron(III) center by binding over the pore of the hydroxylase. The regulatory component then displaces the reductase, docking onto the same surface of the hydroxylase. Formation of the hydroxylase-regulatory component complex (i) induces conformational changes of pore residues that may bring protons to the

  14. The hydrocarbon sphere

    Energy Technology Data Exchange (ETDEWEB)

    Mandev, P.

    1984-01-01

    The hydrocarbon sphere is understood to be the area in which hydrocarbon compounds are available. It is believed that the lower boundary on the hydrocarbon sphere is most probably located at a depth where the predominant temperatures aid in the destruction of hydrocarbons (300 to 400 degrees centigrade). The upper limit on the hydrocarbon sphere obviously occurs at the earth's surface, where hydrocarbons oxidize to H20 and CO2. Within these ranges, the occurrence of the hydrocarbon sphere may vary from the first few hundred meters to 15 kilometers or more. The hydrocarbon sphere is divided into the external (mantle) sphere in which the primary gas, oil and solid hydrocarbon fields are located, and the internal (metamorphic) sphere containing primarily noncommercial accumulations of hydrocarbon gases and solid carbon containing compounds (anthraxilite, shungite, graphite, etc.) based on the nature and scale of hydrocarbon compound concentrations (natural gas, oil, maltha, asphalt, asphaltite, etc.).

  15. Kinase-Catalyzed Biotinylation

    OpenAIRE

    Senevirathne, Chamara; Green, Keith D.; Pflum, Mary Kay H.

    2012-01-01

    Kinase-catalyzed protein phosphorylation plays an essential role in a variety of biological processes. Methods to detect phosphoproteins and phosphopeptides in cellular mixtures will aid in cell biological and signaling research. Our laboratory recently discovered the utility of γ-modified ATP analogues as tools for studying phosphorylation. Specifically, ATP-biotin can be used for labeling and visualizing phosphoproteins from cell lysates. Because the biotin tag is suitable for protein detec...

  16. A modified microbial adhesion to hydrocarbons assay to account for the presence of hydrocarbon droplets.

    Science.gov (United States)

    Zoueki, Caroline Warne; Tufenkji, Nathalie; Ghoshal, Subhasis

    2010-04-15

    The microbial adhesion to hydrocarbons (MATH) assay has been used widely to characterize microbial cell hydrophobicity and/or the extent of cell adhesion to hydrophobic liquids. The classical MATH assay involves spectrophotometric absorbance measurements of the initial and final cell concentrations in an aqueous cell suspension that has been contacted with a hydrocarbon liquid. In this study, microscopic examination of the aqueous cell suspension after contact with hexadecane or a hexadecane/toluene mixture revealed the presence of hydrocarbon droplets. The hydrocarbon droplets contributed to the absorbance values during spectrophotometric measurements and caused erroneous estimates of cell concentrations and extents of microbial adhesion. A modified MATH assay that avoids such artefacts is proposed here. In this modified assay, microscopic examination of the aqueous suspension and direct cell counts provides cell concentrations that are free of interference from hydrocarbon droplets. The presence of hydrocarbon droplets was noted in MATH assays performed with three bacterial strains, and two different hydrocarbons, at ionic strengths of 0.2 mM and 20 mM and pH 6. In these experiments, the formation of quasi-stable hydrocarbon droplets cannot be attributed to the presence of biosurfactants, or stabilization by biocolloids. The presence of surface potential at the hydrocarbon-water interface that was characterized by electrophoretic mobility of up to -1 and -2 microm cm/Vs, likely caused the formation of the quasi-stable hydrocarbon droplets that provided erroneous results using the classical MATH assay. PMID:20129613

  17. Influence of oil and gas field operations on spatial and temporal distributions of atmospheric non-methane hydrocarbons and their effect on ozone formation in winter

    OpenAIRE

    R. A. Field; J. Soltis; M. C. McCarthy; Murphy, S.; Montague, D. C.

    2015-01-01

    Emissions from oil and natural gas development during winter in the Upper Green River basin of Wyoming are known to drive episodic ozone (O3) production. Contrasting O3 distributions were observed in the winters of 2011 and 2012, with numerous episodes (hourly O3 ≥ 85 ppbv) in 2011 compared to none in 2012. The lack of O3 episodes in 2012 coincided with a reduction in measured ambient levels of total non-methane hydrocarbons (NMHC). Measurements of speciated NMHC, and oth...

  18. 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...... properties to the widely discussed gold catalysts. Literature results were summarized for alcohol oxidation, epoxidation, amine oxidation, phenol hydroxylation, silane and sulfide oxidation, (side-chain) oxidation of alkyl aromatic compounds, hydroquinone oxidation and cyclohexane oxidation. It was found...

  19. Hydrocarbon habitat in rifted basins

    Energy Technology Data Exchange (ETDEWEB)

    Ziegler, P.A. [Basel Univ. (Switzerland)

    1996-12-01

    Tectonically active rifts, palaeo-rifts and passive margin basins contain major hydrocarbon provinces. Their hydrocarbon charge can rely exclusively on pre-rift, syn-rift sedimentary sequences or a combination thereof. Maturation of source-rocks can be achieved during the syn-and/or post-rift stage of basin evolution. During rifting, conductive and convective heat transfer accounts for elevated geothermal gradients; these play an important role in the maturation of pre- and syn-rift source-rocks; as geothermal gradients decrease asymptotically during the post-rift stage, maturation of late syn- and post-rift source-rocks depends on massif overburden thicknesses. In most rift structuration and trap-formation predate or are contemporaneous with peak oil and gas generation. Post-rift subsidence and stress-induced basin tilting or inversion can cause modification of trap configurations, causing loss of hydrocarbons. (author). 58 refs., 1 fig., 1 tab.

  20. Catalyzed Ceramic Burner Material

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Amy S., Dr.

    2012-06-29

    Catalyzed combustion offers the advantages of increased fuel efficiency, decreased emissions (both NOx and CO), and an expanded operating range. These performance improvements are related to the ability of the catalyst to stabilize a flame at or within the burner media and to combust fuel at much lower temperatures. This technology has a diverse set of applications in industrial and commercial heating, including boilers for the paper, food and chemical industries. However, wide spread adoption of catalyzed combustion has been limited by the high cost of precious metals needed for the catalyst materials. The primary objective of this project was the development of an innovative catalyzed burner media for commercial and small industrial boiler applications that drastically reduce the unit cost of the catalyzed media without sacrificing the benefits associated with catalyzed combustion. The scope of this program was to identify both the optimum substrate material as well as the best performing catalyst construction to meet or exceed industry standards for durability, cost, energy efficiency, and emissions. It was anticipated that commercial implementation of this technology would result in significant energy savings and reduced emissions. Based on demonstrated achievements, there is a potential to reduce NOx emissions by 40,000 TPY and natural gas consumption by 8.9 TBtu in industries that heavily utilize natural gas for process heating. These industries include food manufacturing, polymer processing, and pulp and paper manufacturing. Initial evaluation of commercial solutions and upcoming EPA regulations suggests that small to midsized boilers in industrial and commercial markets could possibly see the greatest benefit from this technology. While out of scope for the current program, an extension of this technology could also be applied to catalytic oxidation for volatile organic compounds (VOCs). Considerable progress has been made over the course of the grant

  1. Raman characteristics of hydrocarbon and hydrocarbon inclusions

    Institute of Scientific and Technical Information of China (English)

    ZHANG Nai; TIAN ZuoJi; LENG YingYing; WANG HuiTong; SONG FuQing; MENG JianHua

    2007-01-01

    The Raman spectrograms of hydrocarbon standard samples show that: (1) the Raman spectrogram of normal paraffin has very strong peaks of methyl and methylene (from 2700 cm-1 to 2970 cm-1); (2)branch methyl has the particular peak of 748 cm-1±; (3) six cyclic has the particular peak of 804 cm-1±; (4)phenyl has two particular peaks of 988 cm-1± and 3058 cm-1± and the 988 cm-1± peak is stronger than the 3058 cm-1± peak; and (5) hexene has three alkenyl spectrum peaks of 1294 cm-1±, 1635 cm-1± and 2996 cm-1±, with the 1635 cm-1± peak being the strongest, showing that the number of carbon in hydrocarbon does not affect its Raman spectrogram, and the hydrocarbon molecular structure and base groups affect its Raman spectrogram, the same hydrocarbons (such as normal paraffin) have the same Raman spectrogram; the types (such as CH4, C2H6, C3H8) and the content of hydrocarbon in oil inclusions are not estimated by their characteristic Raman peaks. According to the Raman spectrograms of hydrocarbon compositions, the Raman spectrogram of hydrocarbon inclusion can be divided into five types: saturated hydrocarbon Raman spectrogram, fluoresce Raman spectrogram, saturated hydrocarbon bitumen Raman spectrogram, bitumen Raman spectrogram, and ethane Raman spectrogram.And according to the characteristics of Raman spectrogram, hydrocarbon inclusions can be divided into five types: saturated hydrocarbon inclusion, less saturated hydrocarbon (oil or gas) inclusion,saturated hydrocarbon bitumen inclusion, bitumen inclusion, and methane water inclusion.

  2. Raman characteristics of hydrocarbon and hydrocarbon inclusions

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The Raman spectrograms of hydrocarbon standard samples show that: (1) the Raman spectrogram of normal paraffin has very strong peaks of methyl and methylene (from 2700 cm-1 to 2970 cm-1); (2) branch methyl has the particular peak of 748 cm-1±; (3) six cyclic has the particular peak of 804 cm-1±; (4) phenyl has two particular peaks of 988 cm-1± and 3058 cm-1± and the 988 cm-1± peak is stronger than the 3058 cm-1± peak; and (5) hexene has three alkenyl spectrum peaks of 1294 cm-1±, 1635 cm-1± and 2996 cm-1±, with the 1635 cm-1± peak being the strongest, showing that the number of carbon in hy-drocarbon does not affect its Raman spectrogram, and the hydrocarbon molecular structure and base groups affect its Raman spectrogram, the same hydrocarbons (such as normal paraffin) have the same Raman spectrogram; the types (such as CH4, C2H6, C3H8) and the content of hydrocarbon in oil inclu-sions are not estimated by their characteristic Raman peaks. According to the Raman spectrograms of hydrocarbon compositions, the Raman spectrogram of hydrocarbon inclusion can be divided into five types: saturated hydrocarbon Raman spectrogram, fluoresce Raman spectrogram, saturated hydro-carbon bitumen Raman spectrogram, bitumen Raman spectrogram, and ethane Raman spectrogram. And according to the characteristics of Raman spectrogram, hydrocarbon inclusions can be divided into five types: saturated hydrocarbon inclusion, less saturated hydrocarbon (oil or gas) inclusion, saturated hydrocarbon bitumen inclusion, bitumen inclusion, and methane water inclusion.

  3. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    Science.gov (United States)

    Ranney, April P; Ziemann, Paul J

    2016-04-28

    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed. PMID:27043733

  4. Methane Conversion to C2 Hydrocarbons Using Glow Discharge Plasma

    Institute of Scientific and Technical Information of China (English)

    HU Miao; CHEN Jierong

    2007-01-01

    The infrared emission spectra of methane, H', CH and C2 hydrocarbons in natural gas were measured. The process of methane decomposition and C2 hydrocarbons formation was investigated. The experiment showed that the time and conditions of methane decomposition and C2 hydrocarbons formation were different. Methane conversion rate increased with the increase in the current and decrease in the amount of methane. Furthermore, an examination of the reaction mechanisms revealed that free radicals played an important role in the chain reaction.

  5. Cold fusion catalyzed by muons and electrons

    International Nuclear Information System (INIS)

    Two alternative methods have been suggested to produce fusion power at low temperature. The first, muon catalyzed fusion or MCF, uses muons to spontaneously catalyze fusion through the muon mesomolecule formation. Unfortunately, this method fails to generate enough fusion energy to supply the muons, by a factor of about ten. The physics of MCF is discussed, and a possible approach to increasing the number of MCF fusions generated by each muon is mentioned. The second method, which has become known as ''Cold Fusion,'' involves catalysis by electrons in electrolytic cells. The physics of this process, if it exists, is more mysterious than MCF. However, it now appears to be an artifact, the claims for its reality resting largely on experimental errors occurring in rather delicate experiments. However, a very low level of such fusion claimed by Jones may be real. Experiments in cold fusion will also be discussed

  6. Palladium-Catalyzed Environmentally Benign Acylation.

    Science.gov (United States)

    Suchand, Basuli; Satyanarayana, Gedu

    2016-08-01

    Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp(2) C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone. PMID:27377566

  7. Formation and destruction of Polycyclic Aromatic Hydrocarbons (PAHs in the flaring of the biogas collected from an automotive shredded residues landfill

    Directory of Open Access Journals (Sweden)

    Massimo Raboni

    2016-03-01

    Full Text Available The paper shows the results of the combustion in an enclosed flare of the biogas collected from an automotive shredded residues landfill. The results demonstrate that at 1,000°C and long combustion, several synthesis reactions lead to the formation of 4 to 6 rings of PAHs. This formation also involves the formation of compounds such as benzo(g,h,iperylene, indeno(1,2,3-cdpyrene and dibenzo(a,hanthracene not present in raw biogas. However, the compounds most likely to form in combustion are benzo (a anthracene and benzo (b fluoranthene. The only exception is chrysene which is significantly destroyed. The experience has proved the total lack of formation of PAHs with only 2 and 3 aromatic rings.

  8. Supported metal nanoparticles for the remediation of chlorinated hydrocarbons

    Science.gov (United States)

    Schrick, Bettina

    Zero valent iron filings are currently being used in pilot scale field studies to dehalogenate toxic chlorinated hydrocarbons from contaminated surface- and groundwater. Iron filings reduce trichloroethylene (TCE), a model contaminant, via two interconnected degradation pathways: (a) reductive beta-elimination and (b) sequential hydrogenolysis, in which each chlorine atom is sequentially replaced by hydrogen. For the latter pathway, problems arise because the dehalogenation rate decreases as the number of chlorine atoms in the molecule decreases. Therefore, some of the products formed, such as vinyl chloride (VC), are more toxic than the parent compound (TCE), and are only slowly reduced by iron. To improve the rate, cost and technique of remediation for chlorinated hydrocarbons, zero valent nickel-iron (Ni-Fe) nanoparticles have been developed. To elucidate the dehalogenation reaction and particularly the product distributions from a mechanistic standpoint, the roles that nickel and iron play in the dehalogenation of TCE were studied. On the bimetallic particles, the reaction occurs by nickel-catalyzed hydrodechlorination. As the iron actively corrodes, the cathodically protected nickel surface chemisorbs hydrogen ions, and TCE adsorbed to the Ni surface is thus hydrogenated. This reaction competes kinetically with the evolution of molecular hydrogen. Hydrogenolysis of the C-Cl bond results in the formation of linear, as well as branched saturated and unsaturated hydrocarbons. Dispersing the nanometals onto high surface area supports, such as hydrophilic carbon or polyacrylic acid (PAA), provides a delivery vehicle for the reactive nanoparticles. The support acts as a nanometal carrier, and may also help preconcentrate the toxins, and provide a conductive pathway for electron transfer. In general, supports are expected to stabilize the nanoparticles and give an increased surface to volume ratio. The carbon- and PAA-supported nanometals form a permanent suspension

  9. Current Situation and Application in Coal- Generated Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    YANG Guang; XU Hongdong

    2001-01-01

    The characteristics and research methods of terrigenous organic hydrocarbon - generated source rock in coal measures are studied in this thesis. After abundance of organic matters, pyrolysis parameter of rocks and hydrocarbon generated capacity of macerals are basically discussed in coal measures of the Cretaceous Muleng- Chengzihe formation in Suibin depression in Sanjang basin, the hydrocarbon generated grade in coal- generated source rock is ascertained in this depression. At last, we think that it is a main attack prospect in coal - generated hydrocarbons study in the future to research the macerals of coal measures organic source rock and to build a criterion to classify the coal- generated hydrocarbons in Northeast region.

  10. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    time and in combination with other social processes establish more aligned and standardized environmental performance between countries. However, examples of the introduction of environmental management suggests that EMS’ only plays a minor role in developing the actual environmental objectives......This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved...... they are implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  11. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou

    2015-12-01

    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  12. Recent advances in copper-catalyzed asymmetric coupling reactions

    Science.gov (United States)

    2015-01-01

    Summary Copper-catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds. PMID:26734106

  13. Diversity synthesis using the complimentary reactivity of rhodium(II)- and palladium(II)-catalyzed reactions.

    Science.gov (United States)

    Ni, Aiwu; France, Jessica E; Davies, Huw M L

    2006-07-21

    Rhodium(II)-catalyzed reactions of aryldiazoacetates can be conducted in the presence of iodide, triflate, organoboron, and organostannane functionality, resulting in the formation of a variety of cyclopropanes or C-H insertion products with high stereoselectivity. The combination of the rhodium(II)-catalyzed reaction with a subsequent palladium(II)-catalyzed Suzuki coupling offers a novel strategy for diversity synthesis. PMID:16839138

  14. On-line monitoring of trace compounds in the flue gas of an incineration pilot plant: Formation of polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Laser mass spectrometry is applied for on-line analysis of PAHs from a complex flue gas matrix in the combustion chamber of an incineration plant. Process monitoring of industrial processes can be performed. New insights into the formation of toxic combustion byproducts are possible

  15. Process for producing hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Doi, K.; Komatsu, A.; Moroe, M.; Moroe, T.

    1980-07-22

    A process is described for producing a hydrocarbon product consisting essentially of hydrocarbons having about 10 to 50 carbon atoms with 60% or more of said product consisting of hydrocarbons containing 25 to 32 carbon atoms which comprises subjecting a synthetic polyisoprene rubber having 92 to 97% cis-type double bods to a thermally destructive distillation at about 300 to 400/sup 0/ C for about 30 minutes under a reduced pressure of about 0.1 to 5 mm. Hg to obtain said hydrocarbon product consisting essentially of hydrocarbons having about 10 to 50 carbon atoms with 60% or more of said product consisting of hydrocarbons containing 25 to 35 carbon atoms, said hydrocarbon product not having a bad odor and containing scarcely any resinous material.

  16. Towards a methanol economy: Zeolite catalyzed production of synthetic fuels

    DEFF Research Database (Denmark)

    Mentzel, Uffe Vie

    The main focus of this thesis is zeolite catalyzed conversion of oxygenates to hydrocarbon fuels and chemicals. Furthermore, conversion of ethane to higher hydrocarbons has also been studied. After a brief introduction to the concept of “the methanol economy” in the first chapter, the second...... chapter is a literature study of Mobil’s “methanol to hydrocarbons” (MTH) process, giving an overview of the history of the process, the nature of the employed catalysts, and the reaction mechanism. In the third chapter, a series of experiments concerning co conversion of ethane and methanol over a...... commercial H-ZSM-5 zeolite impregnated with gallium and/or molybdenum is described. The object was to investigate if the presence of methanol in the feed could enhance the conversion of ethane, but in all cases the opposite is observed; the presence of methanol actually suppresses the conversion of ethane...

  17. Mechanism of carbon monoxide reactions under high pressure catalyzed by acids and bases

    Energy Technology Data Exchange (ETDEWEB)

    Takezaki, Y.

    1978-05-01

    A review, based mainly on work done at Kyoto University, covers the mechanisms and kinetics of acid-catalyzed carbonylations, including the hydrogen fluoride-catalyzed addition of carbon monoxide to methallyl chloride, the sulfuric acid-catalyzed synthesis of succinic acid from acrylic acid, and the conversion of toluene to p-tolualdehyde in hydrogen fluoride/boron trifluoride by the Gattermann-Koch reaction; and of base-catalyzed reactions, including the production of methyl formate from methanol with 1,8-diazabicyclo (5,4,0)undec-7-ene catalyst and of malonic acid from potassium acetate and potassium carbonate. Graphs, tables, and 34 references.

  18. Renewable synthesis-gas-production. Do hydrocarbons in the reactant flow of the reverse water-gas shift reaction cause coke formation?

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, A.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2013-11-01

    In a two-step synthetic fuel production process based on carbon dioxide and renewable hydrogen, the best possible selectivity towards liquid hydrocarbons (Hc) shall be implemented. The process consists of a combination of the Reverse Water-Gas Shift reaction and the Fischer-Tropsch synthesis. To achieve this goal, gaseous short-chained Hc from the FTS reactor are recycled in the RWGS unit. In this paper, challenges coming up with the implementation of a recycle loop are discussed. First of all, it has to be examined whether Hc are converted under conditions present in the RWGS reactor. The coking caused by the recycle of Hc is regarded, including thermal coking in the heating zone of the reactor and catalytic coking in the catalyst bed. Coking of course is unwanted, as it deactivates the catalyst. The scope of this work is to find out to which extent and under which conditions gaseous Hc can be recycled. Therefore, experiments were carried out in both, a quartz glass reactor using a commercial Ni-catalyst at ambient pressure and in a pressurized steel reactor (without catalyst) to examine coking during the thermal decomposition of Hc. The catalytic experiments at atmospheric pressure showed that a recycle of CH{sub 4} did not cause coking up to a ratio of CH{sub 4}/CO{sub 2} below one. For these conditions, long term stability was proved. The reaction rates of the CH{sub 4} conversion were below those of the RWGS reaction. However, replacing CH{sub 4} by C{sub 3}H{sub 8} leads to thermal and catalytic coking. Catalytic coking hits the maximum level at about 700 C and decreases for higher temperatures and, thus is not regarded as a problem for the RWGS reactor. In contrast to that, thermal coking raises with higher temperatures, but it can be supressed efficiently with additional injection of H{sub 2}O, which of course shifts the equilibrium towards the undesired reactant side. (orig.)

  19. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U;

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two met...

  20. A Palladium-catalyzed Synthesis of 2-Substituted Indoles

    OpenAIRE

    Kasahara, Akira; YANAI, Hiroshi; Murakami, Satoshi

    1986-01-01

    Abstract In the presence of palladium (II) acetate, tri-o-tolylphosphine, and triethylamine, o-bromoaniline derivatives react readily with olefins such as ethylene, 1-hexene, styrene, ethyl acrylate, and acrylonitriIe, to produce o-alkenylaniline derivatives. A palladium (II) -catalyzed cyclization of o-alkenylaniline p-toluenesulfonamide led to a formation of a number of 1-tosylindole derivatives.

  1. Clathrate-hydrate formation from a hydrocarbon gas mixture: Compositional evolution of formed hydrate during an isobaric semi-batch hydrate-forming operation

    International Nuclear Information System (INIS)

    Highlights: • Reports laboratory experiments of hydrate formation from synthetic natural gas. • Shows how hydrate composition changes during each hydrate-forming operation. • Compares the observed compositional change with thermodynamic simulations. • Shows a PXRD result indicating simultaneous formation of sI and sII hydrates. - Abstract: The clathrate hydrate formation from a model natural gas, i.e., a mixture of methane, ethane, and propane in a 90:7:3 molar ratio, under a constant pressure was experimentally investigated, focusing on the compositional evolution of hydrate crystals formed inside a gas-bubbling-type reactor during each semi-batch hydrate-forming operation. The experimental system used in this study was specially designed for obtaining several hydrate samples formed at different, arbitrarily selected stages during each hydrate-forming operation. Each hydrate sample was analyzed by a gas-chromatograph to determine the mole fractions of methane, ethane and propane encaged in the hydrate. These analyses revealed a monotonic increase in the methane fraction and decreases in the ethane and propane fractions during each operation until a quasi-steady state was established. Powder X-ray diffraction analyses showed that both structure-I and structure-II crystals were simultaneously formed during the quasi-steady period. The compositional evolution of the hydrates formed during the early stages before the quasi-steady state was reached deviated from corresponding predictions based on the thermodynamic-simulation scheme previously reported. A hypothetical explanation for the discrepancy between the experimental and simulation-based results was provided

  2. Hydrocarbon utilization by Brevibacterium, Azotomonas, Protaminobacterium, Mycococcus and Aeromonas spp

    Energy Technology Data Exchange (ETDEWEB)

    Lonsane, B.K.; Vadalkar, K.; Singh, H.D.; Baruah, J.N.

    1976-11-01

    Morphological, cultural and biochemical characteristics of 7 bacterial isolates, capable of utilizing hydrocarbons as sole source of carbon, reveal that 3 isolates belong to genus Aeromonas and one each to genera Brevibacterium, Protaminobacter, Mycococcus and Azotomonas. The isolates are studied for biomass formation on gas oil, substrate specificities for petroleum hydrocarbons and fermentation of gas oil by Brevibacterium sp. The hydrocarbon utilizing abilities of the strains of Protaminobacter, Azotomonas and Aeromonas are not known previously.

  3. Treating tar sands formations with dolomite

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J.; Karanikas, John Michael

    2010-06-08

    Methods for treating a tar sands formation are described herein. The tar sands formation may include dolomite and hydrocarbons. Methods may include providing heat at less than the decomposition temperature of dolomite from one or more heaters to at least a portion of the formation. At least some of the hydrocarbon fluids are mobilized in the formation. At least some of the hydrocarbon fluids may be produced from the formation.

  4. Novel CO2 Foam Concepts and Injection Schemes for Improving CO2 Sweep Efficiency in Sandstone and Carbonate Hydrocarbon Formations

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Quoc [Univ. of Texas, Austin, TX (United States). Department of Petroleum & Geosystems Engineering; Hirasaki, George [Rice Univ., Houston, TX (United States). Department of Chemical Engineering; Johnston, Keith [Univ. of Texas, Austin, TX (United States). Department of Chemical Engineering

    2015-02-05

    We explored cationic, nonionic and zwitterionic surfactants to identify candidates that have the potential to satisfy all the key requirements for CO2 foams in EOR. We have examined the formation, texture, rheology and stability of CO2 foams as a function of the surfactant structure and formulation variables including temperature, pressure, water/CO2 ratio, surfactant concentration, salinity and concentration of oil. Furthermore, the partitioning of surfactants between oil and water as well as CO2 and water was examined in conjunction with adsorption measurements on limestone by the Hirasaki lab to develop strategies to optimize the transport of surfactants in reservoirs.

  5. Catalytic hydrocarbon reactions over supported metal oxides. Final report, August 1, 1986--July 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-10-20

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. The approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. The current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. During the course of these studies the author has: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by metathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  6. Towards an understanding of the role of clay minerals in crude oil formation, migration and accumulation

    Science.gov (United States)

    Wu, Lin Mei; Zhou, Chun Hui; Keeling, John; Tong, Dong Shen; Yu, Wei Hua

    2012-12-01

    This article reviews progress in the understanding of the role of clay minerals in crude oil formation, migration and accumulation. Clay minerals are involved in the formation of kerogen, catalytic cracking of kerogen into petroleum hydrocarbon, the migration of crude oil, and the continued change to hydrocarbon composition in underground petroleum reservoirs. In kerogen formation, clay minerals act as catalysts and sorbents to immobilize organic matter through ligand exchange, hydrophobic interactions and cation bridges by the mechanisms of Maillard reactions, polyphenol theory, selective preservation and sorptive protection. Clay minerals also serve as catalysts in acid-catalyzed cracking of kerogen into petroleum hydrocarbon through Lewis and Brønsted acid sites on the clay surface. The amount and type of clay mineral affect the composition of the petroleum. Brønsted acidity of clay minerals is affected by the presence and state of interlayer water, and displacement of this water is a probable driver in crude oil migration from source rocks. During crude oil migration and accumulation in reservoirs, the composition of petroleum is continually modified by interaction with clay minerals. The clays continue to function as sorbents and catalysts even while they are being transformed by diagenetic processes. The detail of chemical interactions and reaction mechanisms between clay minerals and crude oil formation remains to be fully explained but promises to provide insights with broader application, including catalytic conversion of biomass as a source of sustainable energy into the future.

  7. Muon-catalyzed fusion theory: Introduction and review

    International Nuclear Information System (INIS)

    Muon-catalyzed fusion (μCF) has proved to be a fruitful subject for basic physics research as well as a source of cold nuclear fusion. Experiments have demonstrated that over 100 fusions per muon can be catalyzed by formation of the dtμ molecule in mixtures of deuterium and tritium. After a brief review of the subject's history, the dtμ catalysis cycle and the principal relations used in its analysis are described. Some of the important processes in the μCF cycle are then discussed. Finally, the status of current research is appraised. 52 refs., 7 figs

  8. Theoretical survey of muon catalyzed fusion

    International Nuclear Information System (INIS)

    The main steps in the muon-catalyzed d-t fusion cycle are given in this report. Most of the stages are very fast, and therefore do not contribute significantly to the cycling time. Thus at liquid H2 densities (/phi/ = 1 in the standard convention) the time for stopping the negative muon, its subsequent capture and deexcitation to the ground state is estimated to be /approximately/ 10/sup/minus/11/ sec.1 The muon spends essentially all of its time in either the (dμ) ground state, waiting for transfer to a (tμ) ground state to occur, or in the (tμ) ground state, writing for molecular formation to occur. Following the formation of this ''mesomolecule'' (actually a muonic molecular ion), deexcitation and fusion are again fast. Then the muon is (usually) liberated to go around again. We will discuss these steps in some detail. 5 refs., 3 figs

  9. Sulfonate to hydrocarbon ratio influencing thermostability of micellar dispersions

    Energy Technology Data Exchange (ETDEWEB)

    Davis, J.A. Jr.; Kunzman, W.J.

    1970-02-03

    Thermostability of micellar dispersions containing hydrocarbon, aqueous medium, and surfactant can be shifted to higher temperatures by increasing the ratio of surfactant to hydrocarbon within the micellar dispersion. Such dispersions are useful to recover crude oil in a tertiary oil recovery process wherein the temperature of the subterranean formation is as high as 200$F or more. For example, a subterranean formation at a temperature above about 80$F can be flooded by designing the surfactant to hydrocarbon ratio within the micellar dispersion to be stable at the temperature of the formation. (16 claims)

  10. Process for recovering hydrocarbons from hydrocarbon-containing biomass

    Energy Technology Data Exchange (ETDEWEB)

    Dzadzic, P.M.; Price, M.C.; Shih, C.J.; Weil, T.A.

    1982-07-06

    A process is disclosed for enzymatically converting whole plant biomass containing hydrocarbon-containing laticifers to soluble sugars and recovering hydrocarbons in increased yields. The process comprises hydrolyzing whole plant cellulosic material in the presence of enzymes, particularly cellulase, hemicellulase, and pectinase, to produce a hydrocarbon product and recovering from the hydrolysis products a major proportion of the cellulase, hemicellulase and pectinase enzymes for reuse. At least some portion of the required make-up of cellulase, hemicellulase and pectinase enzymes is produced in a two-stage operation wherein, in the first stage, a portion of the output sugar solution is used to grow enzyme secreting microorganisms selected from the group consisting of cellulase-secreting microorganisms, hemicellulase-secreting microorganisms, pectinase-secreting microorganisms, and mixtures thereof, and in the second stage, cellulase, hemicellulase and pectinase enzyme formation is induced in the microorganism-containing culture medium by the addition of an appropriate inducer such as biomass. The cellulase, hemicellulase and pectinase enzymes are then recycled for use in the hydrolysis reaction.

  11. Using Simple Donors to Drive the Equilibria of Glycosyltransferase-Catalyzed Reactions

    OpenAIRE

    Gantt, Richard W.; Peltier-Pain, Pauline; Cournoyer, William J.; Thorson, Jon S.

    2011-01-01

    We report the ability of simple glycoside donors to drastically shift the equilibria of glycosyltransferase-catalyzed reactions, transforming NDP-sugar formation from an endo- to an exothermic process. To demonstrate the utility of this thermodynamic adaptability, we highlight the glycosyltransferase-catalyzed synthesis of 22 sugar nucleotides from simple aromatic sugar donors as well as the corresponding in situ formation of sugar nucleotides as a driving force in context of glycosyltransfer...

  12. The Structural Basis of Ribozyme-Catalyzed RNA Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, M.P.; Scott, W.G.; /UC, Santa Cruz

    2007-07-12

    Life originated, according to the RNA World hypothesis, from self-replicating ribozymes that catalyzed ligation of RNA fragments. We have solved the 2.6 angstrom crystal structure of a ligase ribozyme that catalyzes regiospecific formation of a 5' to 3' phosphodiester bond between the 5'-triphosphate and the 3'-hydroxyl termini of two RNA fragments. Invariant residues form tertiary contacts that stabilize a flexible stem of the ribozyme at the ligation site, where an essential magnesium ion coordinates three phosphates. The structure of the active site permits us to suggest how transition-state stabilization and a general base may catalyze the ligation reaction required for prebiotic RNA assembly.

  13. Analysis and new predictive approach of the phenomenon of a third phase formation in the extraction systems (alkyl-malonamide/hydrocarbon/acid/water)

    International Nuclear Information System (INIS)

    In the framework of spent fuel reprocessing, the DIAMEX process considered for the separation of actinides(III), uses dimethyl-dibutyl-tetra-decyl-malonamide (called DMDBTDMA) as extractant. The main problem encountered in this process is the formation of a third phase in some conditions of acidity of the aqueous phase to be treated. The aim of this work is then to study this phenomenon, on a physico-chemical point of view and to develop a model for anticipating the de-mixing. Analyses have allowed to specify by appropriated techniques, the composition of the organic phases before and after the de-mixing. They indicate that at strong acidities, the third phase contains the quasi totality of the extractant and of the extracted water and acid while the phase floating on the surface is very rich into solvent. The stereochemical study of diamide by NMR has shown that the Z conformation is always majority and becomes still more majority in the third phase. The rotation barriers of the amide function have been specified. The DMDBTDMA molecule is organized under the form of inverse aggregates which join just before the de-mixing as indicate the observed breaks in the surface tension curves. Tests have been carried out to characterize the polarity of the aggregates which have a role in the agglomeration process. A theoretical process has been developed from the Flory-Huggins theory and the solubility parameters. This approach leads to the calculation of χ12, a solvent/aggregate interaction parameter. The correlation of χ12 with the acidity allows to attribute to the extractant a solubility parameter depending on its protonation state. The model anticipates correctly the curve and the effect of few parameters on this ones (acidity, nature of the solvent, temperature, nature of the anions in solution), while taking into account the agglomeration number of the DMDBTDMA, estimated between 5 and 10. (O.M.)

  14. Evaluation of hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Cashman, P.H.; Trexler, J.H. Jr. [Univ. of Nevada, Reno, NV (United States)

    1992-09-30

    Task 8 is responsible for assessing the hydrocarbon potential of the Yucca Mountain vincinity. Our main focus is source rock stratigraphy in the NTS area in southern Nevada. (In addition, Trexler continues to work on a parallel study of source rock stratigraphy in the oil-producing region of east central Nevada, but this work is not funded by Task 8.) As a supplement to the stratigraphic studies, we are studying the geometry and kinematics of deformation at NTS, particularly as these pertain to reconstructing Paleozoic stratigraphy and to predicting the nature of the Late Paleozoic rocks under Yucca Mountain. Our stratigraphic studies continue to support the interpretation that rocks mapped as the {open_quotes}Eleana Formation{close_quotes} are in fact parts of two different Mississippian units. We have made significant progress in determining the basin histories of both units. These place important constraints on regional paleogeographic and tectonic reconstructions. In addition to continued work on the Eleana, we plan to look at the overlying Tippipah Limestone. Preliminary TOC and maturation data indicate that this may be another potential source rock.

  15. Hydrocarbon Spectral Database

    Science.gov (United States)

    SRD 115 Hydrocarbon Spectral Database (Web, free access)   All of the rotational spectral lines observed and reported in the open literature for 91 hydrocarbon molecules have been tabulated. The isotopic molecular species, assigned quantum numbers, observed frequency, estimated measurement uncertainty and reference are given for each transition reported.

  16. Oxygenated Derivatives of Hydrocarbons

    Science.gov (United States)

    For the book entitled “Insect Hydrocarbons: Biology, Biochemistry and Chemical Ecology”, this chapter presents a comprehensive review of the occurrence, structure and function of oxygenated derivatives of hydrocarbons. The book chapter focuses on the occurrence, structural identification and functi...

  17. Dihydrodiol dehydrogenase and polycyclic aromatic hydrocarbon metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Smithgall, T.E.

    1986-01-01

    Carcinogenic activation of polycyclic aromatic hydrocarbons by microsomal monoxygenases proceeds through trans-dihydrodiol metabolites to diol-epoxide ultimate carcinogens. This thesis directly investigated the role of dihydrodiol dehydrogenase, a cytosolic NAD(P)-linked oxidoreductase, in the detoxification of polycyclic aromatic trans-dihydrodiols. A wide variety of non-K-region trans-dihydrodiols were synthesized and shown to be substrates for the homogeneous rat liver dehydrogenase, including several potent proximate carcinogens derived from 7,12-dimethylbenz(a)anthracene, 5-methylchrysene, and benzo(a)pyrene. Since microsomal activation of polycyclic aromatic hydrocarbons is highly stereospecific, the stereochemical course of enzymatic trans-dihydrodiol oxidation was monitored using circular dichroism spectropolarimetry. The major product formed from the dehydrogenase-catalyzed oxidation of the trans-1,2-dihydrodiol of naphthalene was characterized using UV, IR, NMR, and mass spectroscopy, and appears to be 4-hydroxy-1,2-naphthoquinone. Mass spectral analysis suggests that an analogous hydroxylated o-quinone is formed as the major product of benzo(a)pyrene-7,8-dihydrodiol oxidation. Enzymatic oxidation of trans-dihydrodiols was shown to be potently inhibited by all of the major classes of the nonsteroidal antiinflammatory drugs. Enhancement of trans-dihydrodiol proximate carcinogen oxidation may protect against possible adverse effects of the aspirin-like drugs, and help maintain the balance between activation and detoxification of polycyclic aromatic hydrocarbons.

  18. Metformin inhibits 7,12-dimethylbenz[a]anthracene-induced breast carcinogenesis and adduct formation in human breast cells by inhibiting the cytochrome P4501A1/aryl hydrocarbon receptor signaling pathway

    International Nuclear Information System (INIS)

    Recent studies have established that metformin (MET), an oral anti-diabetic drug, possesses antioxidant activity and is effective against different types of cancer in several carcinogen-induced animal models and cell lines. However, whether MET can protect against breast cancer has not been reported before. Therefore, the overall objectives of the present study are to elucidate the potential chemopreventive effect of MET in non-cancerous human breast MCF10A cells and explore the underlying mechanism involved, specifically the role of cytochrome P4501A1 (CYP1A1)/aryl hydrocarbon receptor (AhR) pathway. Transformation of the MCF10A cells into initiated breast cancer cells with DNA adduct formation was conducted using 7,12-dimethylbenz[a]anthracene (DMBA), an AhR ligand. The chemopreventive effect of MET against DMBA-induced breast carcinogenesis was evidenced by the capability of MET to restore the induction of the mRNA levels of basic excision repair genes, 8-oxoguanine DNA glycosylase (OGG1) and apurinic/apyrimidinic endonuclease1 (APE1), and the level of 8-hydroxy-2-deoxyguanosine (8-OHdG). Interestingly, the inhibition of DMBA-induced DNA adduct formation was associated with proportional decrease in CYP1A1 and in NAD(P)H:quinone oxidoreductase 1 (NQO1) gene expression. Mechanistically, the involvements of AhR and nuclear factor erythroid 2-related factor-2 (Nrf2) in the MET-mediated inhibition of DMBA-induced CYP1A1 and NQO1 gene expression were evidenced by the ability of MET to inhibit DMBA-induced xenobiotic responsive element and antioxidant responsive element luciferase reporter gene expression which suggests an AhR- and Nrf2-dependent transcriptional control. However, the inability of MET to bind to AhR suggests that MET is not an AhR ligand. In conclusion, the present work shows a strong evidence that MET inhibits the DMBA-mediated carcinogenicity and adduct formation by inhibiting the expression of CYP1A1 through an AhR ligand-independent mechanism

  19. Metformin inhibits 7,12-dimethylbenz[a]anthracene-induced breast carcinogenesis and adduct formation in human breast cells by inhibiting the cytochrome P4501A1/aryl hydrocarbon receptor signaling pathway

    Energy Technology Data Exchange (ETDEWEB)

    Maayah, Zaid H. [Department of Pharmacology and Toxicology, College of Pharmacy, King Saud University, Riyadh 11451 (Saudi Arabia); Ghebeh, Hazem [Stem Cell & Tissue Re-Engineering, King Faisal Specialist Hospital and Research Center, Riyadh 11211 (Saudi Arabia); Alhaider, Abdulqader A. [Department of Pharmacology and Toxicology, College of Pharmacy, King Saud University, Riyadh 11451 (Saudi Arabia); Camel Biomedical Research Unit, College of Pharmacy and Medicine, King Saud University, Riyadh 11451 (Saudi Arabia); El-Kadi, Ayman O.S. [Faculty of Pharmacy & Pharmaceutical Sciences, University of Alberta, Edmonton (Canada); Soshilov, Anatoly A.; Denison, Michael S. [Department of Environmental Toxicology, University of California at Davis, Davis, CA 95616 (United States); Ansari, Mushtaq Ahmad [Department of Pharmacology and Toxicology, College of Pharmacy, King Saud University, Riyadh 11451 (Saudi Arabia); Korashy, Hesham M., E-mail: hkorashy@ksu.edu.sa [Department of Pharmacology and Toxicology, College of Pharmacy, King Saud University, Riyadh 11451 (Saudi Arabia)

    2015-04-15

    Recent studies have established that metformin (MET), an oral anti-diabetic drug, possesses antioxidant activity and is effective against different types of cancer in several carcinogen-induced animal models and cell lines. However, whether MET can protect against breast cancer has not been reported before. Therefore, the overall objectives of the present study are to elucidate the potential chemopreventive effect of MET in non-cancerous human breast MCF10A cells and explore the underlying mechanism involved, specifically the role of cytochrome P4501A1 (CYP1A1)/aryl hydrocarbon receptor (AhR) pathway. Transformation of the MCF10A cells into initiated breast cancer cells with DNA adduct formation was conducted using 7,12-dimethylbenz[a]anthracene (DMBA), an AhR ligand. The chemopreventive effect of MET against DMBA-induced breast carcinogenesis was evidenced by the capability of MET to restore the induction of the mRNA levels of basic excision repair genes, 8-oxoguanine DNA glycosylase (OGG1) and apurinic/apyrimidinic endonuclease1 (APE1), and the level of 8-hydroxy-2-deoxyguanosine (8-OHdG). Interestingly, the inhibition of DMBA-induced DNA adduct formation was associated with proportional decrease in CYP1A1 and in NAD(P)H:quinone oxidoreductase 1 (NQO1) gene expression. Mechanistically, the involvements of AhR and nuclear factor erythroid 2-related factor-2 (Nrf2) in the MET-mediated inhibition of DMBA-induced CYP1A1 and NQO1 gene expression were evidenced by the ability of MET to inhibit DMBA-induced xenobiotic responsive element and antioxidant responsive element luciferase reporter gene expression which suggests an AhR- and Nrf2-dependent transcriptional control. However, the inability of MET to bind to AhR suggests that MET is not an AhR ligand. In conclusion, the present work shows a strong evidence that MET inhibits the DMBA-mediated carcinogenicity and adduct formation by inhibiting the expression of CYP1A1 through an AhR ligand-independent mechanism

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

    Energy Technology Data Exchange (ETDEWEB)

    Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C. [Univ. of California, Davis, CA (United States)

    1995-12-31

    The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.

  1. 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 photo-de

  2. Manganese Catalyzed C-H Halogenation.

    Science.gov (United States)

    Liu, Wei; Groves, John T

    2015-06-16

    The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

  3. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Directory of Open Access Journals (Sweden)

    Chad C. Eichman

    2011-01-01

    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  4. Hydrocarbon production with nuclear explosives

    International Nuclear Information System (INIS)

    The tremendous energy of nuclear explosives and the small dimensions of the explosive package make an ideal combination for drill-hole explosive emplacement in deep, thick hydrocarbon deposits. Potential applications exist in fracturing low permeability natural-gas and petroleum formations for stimulating production, fracturing oil shale to permit in situ retorting, and creating storage chimneys for natural gas, liquefied petroleum gas, petroleum, petroleum products, helium, and other fluids. Calculations show, for example, that less than 100 shots per year would be needed to stabilize the natural gas reserves to production ratio. Under the Government-industry Plowshare program, two experiments, Projects Gasbuggy and Rulison, were conducted to stimulate natural gas production from low-permeability formations. Incomplete information indicates that both were technically successful. Potential problems associated with the use of nuclear explosives for underground engineering applications are radioactive contamination, maximum yield limitations, high costs of detonating contained nuclear explosives, and adverse public opinion. Results at Project Gasbuggy and other considerations indicated that the problem of radioactive contamination was about as predicted and not an insurmountable one. Also, it was demonstrated that shots at adequate depths could be detonated without appreciable damage to existing surface and subsurface buildings, natural features, and equipment. However, costs must be reduced and the public must be better informed before these techniques can be widely used in field operations. On the basis of present knowledge, the potential of nuclear-explosive stimulation of hydrocarbon production appears good. Additional field experiments will be required to adequately explore that potential. (author)

  5. Polycyclic Aromatic Hydrocarbons

    Science.gov (United States)

    Salama, Farid

    2010-01-01

    Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of the carbonaceous materials. PAHs are the best-known candidates to account for the IR emission bands. They are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge is to reproduce in the laboratory the physical conditions that exist in the emission and absorption interstellar zones. The harsh physical conditions of the ISM -low temperature, collisionless, strong UV radiation fields- are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions and radicals are formed from the neutral precursors in an isolated environment at low temperature and probed with high-sensitivity cavity ringdown spectroscopy in the NUV-NIR range. Carbon nanoparticles are also formed during the short residence time of the precursors in the plasma and are characterized with time-offlight mass spectrometry. These experiments provide unique information on the spectra of large carbonaceous molecules and ions in the gas phase that can now be directly compared to interstellar and circumstellar observations (IR emission bands, DIBs, extinction curve). These findings also hold great potential for understanding the formation process of interstellar carbonaceous grains. We will review recent progress in the experimental and theoretical studies of PAHs, compare the laboratory data with astronomical observations and discuss the global implications.

  6. Thraustochytrid protists degrade hydrocarbons

    Digital Repository Service at National Institute of Oceanography (India)

    Raikar, M.T.; Raghukumar, S.; Vani, V.; David, J.J.; Chandramohan, D.

    isolation tubes with crude oil. Three isolates tested showed positive hydrophobicity of cell walls as judged by the Microbial Adhesion to Hydrocarbons (MATH) assay. Addition of Bombay High crude oil to nutrient broth slightly enhanced growth of the protists...

  7. Immunoassay for petroleum hydrocarbons

    International Nuclear Information System (INIS)

    Petroleum hydrocarbon contamination of soil and ground water has become a serious environmental problem. Since the 1940s, it has been a common practice to bury fuel tanks underground to guard against fire and explosions. The leakage of petroleum fuel from these aging tanks creates a long term threat to human health. In order to location and identify these sources of contamination, an on-site screening test is very desirable. A simple, inexpensive petroleum hydrocarbon immunoassay has been developed for this purpose. The EnviroGard Petroleum Hydrocarbon test kit is designed for qualitative or semiquantitative analysis of petroleum hydrocarbon fuel in soil and ground water. The assay can be easily used on-site and takes 15 minutes to perform. Following a 2 minute methanol extraction, the test is performed in polystyrene tubes and can detect gasoline, diesel fuel, kerosene, home heating oil and other major fuels at ppm levels in soil and sub-ppm levels in water samples

  8. Noble gas and hydrocarbon tracers in multiphase unconventional hydrocarbon systems: Toward integrated advanced reservoir simulators

    Science.gov (United States)

    Darrah, T.; Moortgat, J.; Poreda, R. J.; Muehlenbachs, K.; Whyte, C. J.

    2015-12-01

    Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noble gas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

  9. Green Methodologies to Test Hydrocarbon Reservoirs

    Directory of Open Access Journals (Sweden)

    Francesca Verga

    2010-01-01

    Full Text Available Problem statement: The definition and the economic viability of the best development strategy of a hydrocarbon reservoir mainly depend on the quantity and type of fluids and on the well productivity. Well testing, consisting in producing hydrocarbon to the surface while measuring the pressure variations induced in the reservoir, has been used for decades to determine the fluid nature and well potential. In exploration and appraisal scenarios the hydrocarbons produced during a test are flared, contributing to the emissions of greenhouse gases. Approach: Due to more stringent environmental regulations and a general need for reduced operating expenses, the current industry drivers in today’s formation evaluation methodologies demand short, safe, cost-effective and environmentally friendly test procedures, especially when conventional tests are prohibitively expensive, logistically not feasible or no surface emissions are allowed. Different methods have been proposed or resuscitated in the last years, such as wireline formation tests, closed chamber tests, production/reinjection tests and injection tests, as viable alternatives to conventional well testing. Results: While various short-term tests, test procedures and interpretation methods are apparently available for conducting successful tests without hydrocarbon production at the surface, clarity is lacking for specific applications of these techniques. An attempt to clarify advantages and limitations of each methodology, particularly with respect to the main testing target is pursued in this study. Specific insight is provided on injection testing, which is one of the most promising methodology to replace traditional well testing in reservoir characterization, except for the possibility to sample the formation fluids. Conclusion/Recommendations: Not a single one method but a combination of more methodologies, in particular injection testing and wireline formation testing, is the most promising

  10. An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact-generated gases

    Science.gov (United States)

    Shock, E. L.

    2000-01-01

    Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

  11. Iodine-catalyzed coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, J.T.; Duffield, J.E.; Davidson, M.G. (Amoco Oil Company, Naperville, IL (USA). Research and Development Dept.)

    Coals of two different ranks were liquefied in high yields using catalytic quantities of elemental iodine or iodine compounds. Iodine monochloride was found to be especially effective for enhancing both coal conversion and product quality. It appears that enhancement in coal conversion is due to the unique ability of iodine to catalyze radical-induced bond scission and hydrogen addition to the coal macromolecule or coal-derived free radicals. The starting iodine can be fully accounted for in the reaction products as both organic-bound and water-soluble forms. Unconverted coal and the heavy product fractions contain the majority of the organic-bound iodine. The results of iodine-catalyzed coal reactions emphasize the need for efficient hydrogen atom transfer along with bond scission to achieve high conversion and product quality. 22 refs., 12 tabs.

  12. A Simple Strategy for Glycosyltransferase-Catalyzed Aminosugar Nucleotide Synthesis

    OpenAIRE

    Zhang, Jianjun; Singh, Shanteri; Hughes, Ryan R.; Zhou, Maoquan; Sunkara, Manjula; Morris, Andrew J.; Thorson, Jon S.

    2014-01-01

    A set of 2-chloro-4-nitrophenyl glucosamino/xylosaminosides were synthesized and assessed as potential substrates in the context of glycosyltransferase-catalyzed formation of the corresponding UDP/TDP-α-D-glucosamino-/xylosaminosugars and single vessel transglycosylation reactions with a model acceptor. This study highlights a robust platform for aminosugar nucleotide synthesis and reveals OleD Loki as a proficient catalyst for U/TDP-aminosugar synthesis and utilization.

  13. Lipase-catalyzed polyester synthesis – A green polymer chemistry

    OpenAIRE

    Kobayashi, Shiro

    2010-01-01

    This article is a short comprehensive review describing in vitro polyester synthesis catalyzed by a hydrolysis enzyme of lipase, most of which has been developed for these two decades. Polyesters are prepared by repeated ester bond-formation reactions; they include two major modes, ring-opening polymerization (ROP) of cyclic monomers such as cyclic esters (lactones) and condensation polymerization via the reaction between a carboxylic acid or its ester group and an alcohol group. Polyester sy...

  14. Synthesis of Optically Active Polystyrene Catalyzed by Monophosphine Pd Complexes.

    Science.gov (United States)

    Jouffroy, Matthieu; Armspach, Dominique; Matt, Dominique; Osakada, Kohtaro; Takeuchi, Daisuke

    2016-07-11

    Cationic Pd(II) monophosphine complexes derived from α- and β-cyclodextrins (CDs) promote the homopolymerization of styrene under carbon monoxide pressure. Although reversible CO coordination takes place under catalytic conditions according to (13) C NMR studies with (13) C-enriched CO, both complexes catalyze the formation of CO-free styrene polymers. These macromolecules display optical activity as a result of the presence of stereoregular sequences within the overall atactic polymer. PMID:27218801

  15. Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids

    OpenAIRE

    Yi, Chae S.; Gao, Ruili

    2009-01-01

    The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. Strong solvent effect was observed for the ruthenium catalyst in modulating the activity and selectivity; the coupling reaction in CH2Cl2 led to the regioselective formation of gem-enol ester products, while the stereoselective formation of (Z)-enol esters was obtained in THF. The coupling reaction was ...

  16. Catalytic hydrocarbon reactions over supported metal oxides. Progress report, April 1, 1994--January 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1995-01-31

    Oxide catalysis plays a central role in hydrocarbon processing and improvements in catalytic activity or selectivity are of great technological importance because these improvements will translate directly into more efficient utilization of hydrocarbon supplies and lower energy consumption in separation processes. An understanding of the relationships between surface structure and catalytic properties is needed to describe and improve oxide catalysts. Our approach has been to prepare supported oxides that have a specific structure and oxidation state and then employ these structures in reaction studies. Our current research program is focused on studying the fundamental relationships between structure and reactivity for two important reactions that are present in many oxide-catalyzed processes, partial oxidation and carbon-carbon bond formation. Oxide catalysis can be a complex process with both metal cation and oxygen anions participating in the chemical reactions. From an energy perspective carbon-carbon bond formation is particularly relevant to CO hydrogenation in isosynthesis. Hydrogenolysis and hydrogenation form the basis for heteroatom removal in fuels processing. Understanding the catalysis of these processes (and others) requires isolating reaction steps in the overall cycle and determining how structure and composition influence the individual reaction steps. Specially designed oxides, such as we use, permit one to study some of the steps in oxidation, carbon-carbon coupling and heteroatom removal catalysis. During the course of our studies we have: (1) developed methods to form and stabilize various Mo and W oxide structures on silica; (2) studied C-H abstraction reactions over the fully oxidized cations; (3) studied C-C bond coupling by methathesis and reductive coupling of aldehydes and ketones over reduced cation structures; and (4) initiated a study of hydrogenation and hydrogenolysis over reduced cation structures.

  17. In situ heat treatment of a tar sands formation after drive process treatment

    Science.gov (United States)

    Vinegar, Harold J.; Stanecki, John

    2010-09-21

    A method for treating a tar sands formation includes providing a drive fluid to a hydrocarbon containing layer of the tar sands formation to mobilize at least some hydrocarbons in the layer. At least some first hydrocarbons from the layer are produced. Heat is provided to the layer from one or more heaters located in the formation. At least some second hydrocarbons are produced from the layer of the formation. The second hydrocarbons include at least some hydrocarbons that are upgraded compared to the first hydrocarbons produced by using the drive fluid.

  18. Hydrocarbon accumulation in network and its application in the continental rift basin

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The concept of hydrocarbon accumulation in network was presented on basis of the overall analysis of the formation and evolution characteristics of the continental faulted basin and of the systemic re-search on the major controlling factors on the hydrocarbon accumulation. The hydrocarbon accumu-lation in network can be defined as hydrocarbon accumulation in a three-dimensional network system which is constituted by the hydrocarbon migration passages under multiple dynamics,following the hydrocarbon generation from source rocks. The research shows that the hydrocarbon accumulation in network is composed of four elements,i.e.,hydrocarbon source (source rock kitchen),hydrocarbon accumulation terminal (trap),network pathway connecting source and terminal (transporting system),and network potential driving hydrocarbon migration in the network pathway (migration dynamics). Compared with other networks,hydrocarbon accumulation in network has three basic characteristics: the irreversible geological process of material and information flow in the network; the loss of material and information in the flow process in the network; the multiple dynamics in the flow process. Interac-tion of all the elements in the geological process can be called hydrocarbon accumulation in network. There are three basic models for hydrocarbon accumulation in network,that is,hydrocarbon accumu-lation in the network source area,hydrocarbon accumulation in the network pathway,and hydrocarbon accumulation in the network terminal. The key in the application of the hydrocarbon accumulation models in network in practice is to confirm the major accumulation stage and the function range of the four elements controlling the hydrocarbon firstly,to predict the profitable accumulation region by su-perposition of the favorable areas confirmed by four elements consequently,and to evaluate the oil-bearing property of the trap as well as confirm drilling targets. This paper takes the Dongying De-pression in the

  19. Task 8: Evaluation of hydrocarbon potential

    Energy Technology Data Exchange (ETDEWEB)

    Cashman, P.H.; Trexler, J.H. Jr.

    1994-12-31

    Our studies focus on the stratigraphy of Late Devonian to early Pennsylvanian rocks at the NTS, because these are the best potential hydrocarbon source rocks in the vicinity of Yucca Mountain. In the last year, our stratigraphic studies have broadened to include the regional context for both the Chainman and the Eleana formations. New age data based on biostratigraphy constrain the age ranges of both Chainman and Eleana; accurate and reliable ages are essential for regional correlation and for regional paleogeographic reconstructions. Source rock analyses throughout the Chainman establish whether these rocks contained adequate organic material to generate hydrocarbons. Maturation analyses of samples from the Chainman determine whether the temperature history has been suitable for the generation of liquid hydrocarbons. Structural studies are aimed at defining the deformation histories and present position of the different packages of Devonian - Pennsylvanian rocks. This report summarizes new results of our structural, stratigraphic and hydrocarbon source rock potential studies at the Nevada Test Site and vicinity. Stratigraphy is considered first, with the Chainman Shale and Eleana Formation discussed separately. New biostratigraphic results are included in this section. New results from our structural studies are summarized next, followed by source rock and maturation analyses of the Chainman Shale. Directions for future work are included where appropriate.

  20. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)

    2011-07-01

    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  1. Superconductivity in aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Highlights: • Aromatic superconductor is one of core research subjects in superconductivity. Superconductivity is observed in certain metal-doped aromatic hydrocarbons. Some serious problems to be solved exist for future advancement of the research. This article shows the present status of aromatic superconductors. - Abstract: ‘Aromatic hydrocarbon’ implies an organic molecule that satisfies the (4n + 2) π-electron rule and consists of benzene rings. Doping solid aromatic hydrocarbons with metals provides the superconductivity. The first discovery of such superconductivity was made for K-doped picene (Kxpicene, five benzene rings). Its superconducting transition temperatures (Tc’s) were 7 and 18 K. Recently, we found a new superconducting Kxpicene phase with a Tc as high as 14 K, so we now know that Kxpicene possesses multiple superconducting phases. Besides Kxpicene, we discovered new superconductors such as Rbxpicene and Caxpicene. A most serious problem is that the shielding fraction is ⩽15% for Kxpicene and Rbxpicene, and it is often ∼1% for other superconductors. Such low shielding fractions have made it difficult to determine the crystal structures of superconducting phases. Nevertheless, many research groups have expended a great deal of effort to make high quality hydrocarbon superconductors in the five years since the discovery of hydrocarbon superconductivity. At the present stage, superconductivity is observed in certain metal-doped aromatic hydrocarbons (picene, phenanthrene and dibenzopentacene), but the shielding fraction remains stubbornly low. The highest priority research area is to prepare aromatic superconductors with a high superconducting volume-fraction. Despite these difficulties, aromatic superconductivity is still a core research target and presents interesting and potentially breakthrough challenges, such as the positive pressure dependence of Tc that is clearly observed in some phases of aromatic hydrocarbon superconductors

  2. Stau-catalyzed Nuclear Fusion

    OpenAIRE

    Hamaguchi, K.; Hatsuda, T.(Theoretical Research Division, Nishina Center, RIKEN, Saitama, 351-0198, Japan); Yanagida, T. T.

    2006-01-01

    We point out that the stau may play a role of a catalyst for nuclear fusions if the stau is a long-lived particle as in the scenario of gravitino dark matter. In this letter, we consider d d fusion under the influence of stau where the fusion is enhanced because of a short distance between the two deuterons. We find that one chain of the d d fusion may release an energy of O(10) GeV per stau. We discuss problems of making the stau-catalyzed nuclear fusion of practical use with the present tec...

  3. Gold-catalyzed naphthalene functionalization

    OpenAIRE

    Iván Rivilla; M. Mar Díaz-Requejo; Pedro J. Pérez

    2011-01-01

    The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO2Et (R = H, Me) from N2C(R)CO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either f...

  4. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  5. Laboratory measurements of ion-molecule reactions pertaining to interstellar hydrocarbon synthesis

    International Nuclear Information System (INIS)

    Measurements on a variety of three-body association reactions between hydrocarbon ions and molecular hydrogen in the presence of helium have been undertaken. The rate coefficients of most of the systems studied are vanishingly small (-30 cm6 s-1) even at 80 K. The results cast severe doubt on a recent gas-phase model of complex hydrocarbon formation in dense interstellar clouds in which radiative association reactions between hydrocarbon ions and molecular hydrogen play a key role. In addition to the three-body reactions, some two-body reactions between hydrocarbon ions and molecular hydrogen and some reactions between carbon ions (C+) and hydrocarbon neutrals have been studied

  6. HYDROCARBONS DIAGNOSTIC OF POLLUTED SOILS

    Directory of Open Access Journals (Sweden)

    Mohamed Arad

    2010-12-01

    Full Text Available Petroleum hydrocarbons are known as carcinogenic and may contaminate the environment (water, air and soil. In this study, a diagnostic of polluted soils by petroleum hydrocarbons is carried out in order to know the effect of their accumulation as well as their behavior in time. The aging factor, a source of significant changing in hydrocarbon behavior, is integrated on two sites of an industrial refinery as experimental samples. The first site is recently polluted by hydrocarbons while the second is a previously polluted site.The results indicate that the concentration of hydrocarbons on the surface of the first site is greater and remains stable in time, as for the second site, hydrocarbons concentration on the surface is also important and undergoes a weak reduction. At a depth of one meter hydrocarbons exist at a greater concentration. This shows that obstinate hydrocarbons are an environmental danger for fauna and flora.

  7. Spectroscopic and QM/MM investigations of Chloroperoxidase catalyzed degradation of orange G.

    Science.gov (United States)

    Zhang, Rui; He, Qinghao; Huang, Yi; Wang, Xiaotang

    2016-04-15

    Chloroperoxidase (CPO), a heme-thiolate protein, from Caldariomyces fumago catalyzes a plethora of reactions including halogenation, dismutation, epoxidation, and oxidation. Although all CPO-catalyzed reactions go through a common intermediate, compound I, different mechanisms are followed in subsequent transformations. To understand the mechanism of CPO-catalyzed halide-dependent degradation of orange G, the role of halide and pH was systematically investigated. It is revealed that formation and protonation of compound X, a long-sought after hypochlorite heme adduct intermediate existed during CPO-catalyzed halide-dependent reactions, significantly lowers the reaction barrier and increases the efficiency of CPO-catalyzed orange G degradation. The extremely acidic optimal reaction pH suggests the protonation of a residue, presumably, Glu 183 in CPO catalysis. Halide dependent studies showed that Kcat is higher in the presence of Br(-) than in the presence of Cl(-). The degradation products of orange G indicate the cleavage at a single position of orange G, demonstrating a high regioselectivity of CPO-catalyzed degradation. Based on our kinetic, NMR and QM/MM studies, the mechanism of CPO-catalyzed orange G degradation was proposed. PMID:26926259

  8. Selecting hydrocarbon rocket propulsion technology

    Science.gov (United States)

    Martin, J. A.

    1986-01-01

    Past studies have shown that the dry weight of future earth-to-orbit vehicles can be reduced by the combined use of hydrogen and hydrocarbon propulsion compared to all-hydrogen propulsion. This paper shows that the use of certain hydrocarbon engines with hydrogen engines produces the lowest vehicle dry mass. These hydrocarbon engines use propane or RP-1 fuel, hydrogen cooling, and hydrogen-rich gas generators. Integration of the hydrogen and hydrocarbon nozzles is also beneficial.

  9. HYDROCARBONS DIAGNOSTIC OF POLLUTED SOILS

    OpenAIRE

    Mohamed Arad; Abdelkader Anouzla; Mohamed Safi; Salah Souabi; Hicham Rhbal

    2010-01-01

    Petroleum hydrocarbons are known as carcinogenic and may contaminate the environment (water, air and soil). In this study, a diagnostic of polluted soils by petroleum hydrocarbons is carried out in order to know the effect of their accumulation as well as their behavior in time. The aging factor, a source of significant changing in hydrocarbon behavior, is integrated on two sites of an industrial refinery as experimental samples. The first site is recently polluted by hydrocarbons while the s...

  10. Ti-catalyzed HfSiO4 formation in HfTiO4 films on SiO2 studied by Z-contrast scanning electron microscopy

    Directory of Open Access Journals (Sweden)

    Elizabeth Ellen Hoppe

    2013-08-01

    Full Text Available Hafnon (HfSiO4 as it is initially formed in a partially demixed film of hafnium titanate (HfTiO4 on fused SiO2 is studied by atomic number (Z contrast high resolution scanning electron microscopy, x-ray diffraction, and Raman spectroscopy and microscopy. The results show exsoluted Ti is the catalyst for hafnon formation by a two-step reaction. Ti first reacts with SiO2 to produce a glassy Ti-silicate. Ti is then replaced by Hf in the silicate to produce HfSiO4. The results suggest this behavior is prototypical of other Ti-bearing ternary or higher order oxide films on SiO2 when film thermal instability involves Ti exsolution.

  11. 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.

  12. Cytochrome c catalyzes the in vitro synthesis of arachidonoyl glycine

    International Nuclear Information System (INIS)

    Long chain fatty acyl glycines are an emerging class of biologically active molecules that occur naturally and produce a wide array of physiological effects. Their biosynthetic pathway, however, remains unknown. Here we report that cytochrome c catalyzes the synthesis of N-arachidonoyl glycine (NAGly) from arachidonoyl coenzyme A and glycine in the presence of hydrogen peroxide. The identity of the NAGly product was verified by isotope labeling and mass analysis. Other heme-containing proteins, hemoglobin and myoglobin, were considerably less effective in generating arachidonoyl glycine as compared to cytochrome c. The reaction catalyzed by cytochrome c in vitro points to its potential role in the formation of NAGly and other long chain fatty acyl glycines in vivo

  13. Optrode for sensing hydrocarbons

    Science.gov (United States)

    Miller, Holly; Milanovich, Fred P.; Hirschfeld, Tomas B.; Miller, Fred S.

    1987-01-01

    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.

  14. 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.

  15. Process limitations of a whole-cell P450 catalyzed reaction using a CYP153A-CPR fusion construct expressed in Escherichia coli

    DEFF Research Database (Denmark)

    Lundemo, M. T.; Notonier, S.; Striedner, G.;

    2016-01-01

    Cytochrome P450s are interesting biocatalysts due to their ability to hydroxylate non-activated hydrocarbons in a selective manner. However, to date only a few P450-catalyzed processes have been implemented in industry due to the difficulty of developing economically feasible processes. In this s...

  16. Method and apparatus for pyrolytically cracking hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Skraba, F.W.

    1992-06-09

    This patent describes a method for pyrolytically cracking a hydrocarbon vapor feedstock in a hydrocarbon pyrolysis unit to produce an olefinic hydrocarbon product. It comprises contacting a hydrocarbon vapor feedstock, then, cracking the hydrocarbon vapor feedstock in the presence of the vaporized water in a pyrolysis furnace to produce a furnace effluent stream comprised of an olefinic hydrocarbon product gas and the vaporized water.

  17. Apparatus and methods for hydrocarbon extraction

    Energy Technology Data Exchange (ETDEWEB)

    Bohnert, George W.; Verhulst, Galen G.

    2016-04-26

    Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

  18. Energy additivity in branched and cyclic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Gao, H.; Bader, R.F.W. [McMaster Univ., Hamilton, ON (Canada). Dept. of Chemistry; Cortes-Guzman, F. [Univ. Nacional Autonoma de Mexico, (Mexico). Dept. de Fisicoquimica

    2009-11-15

    This paper reported on a study of the energetic relationships between hydrocarbon molecules and the heats of formation. The quantum theory of atoms in molecules (QTAIM) was used to investigate the degree to which branched hydrocarbons obey a group additivity scheme for energy and populations. The QTAIM defined the properties of the chemical groups. The experimental and theoretical transferability of the methyl and methylene groups of the linear hydrocarbons was also explored. The calculations were performed using a large basis set at the restricted Hartree-Fock and MP2(full) levels of theory. The study also investigated the deviations from additivity, noted for small ring hydrocarbons leading to the definition of strain energy. The QTAIM energies recovered the experimental values. The paper included details regarding the delocalization of the electron density over the surface of the cyclopropane ring, responsible for its homoaromatic properties. The calculations presented in this study satisfied the virial theorem for the atomic definition of energy. The paper discussed the problems associated with the use of the density functional theory (DFT) resulting from its failure to satisfy the virial theorem. 44 refs., 9 tabs., 2 figs.

  19. A three-step process to facilitate the annulation of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Martin, Sara E; Streeter, Matthew D; Jones, Laurel L; Klepfer, Matthew S; Atmatzidis, Kyriakos; Wille, Kristen D; Harrison, Sean A; Hoegg, Edward D; Sheridan, Heather M; Kramer, Stephanie; Parrish, Damon A; Amick, Aaron W

    2014-09-01

    A new efficient three-step process to annulate polycyclic aromatic hydrocarbons (PAHs) has been developed, providing access to PAHs with saturated rings that under current chemical methods would be difficult to produce in an efficient manner. This method relies on a palladium-catalyzed cross-coupling reaction of various brominated PAHs with cyclohexanone to yield α-arylated ketones, which are converted to regiospecific vinyl triflates and cyclized by a palladium-catalyzed intramolecular arene-vinyl triflate coupling to produce PAHs with incorporated saturated rings or "tetrahydroindeno-annulated" PAHs. PMID:25137354

  20. Physics and the Quest for Hydrocarbons

    Science.gov (United States)

    Clark, Brian

    2011-04-01

    This talk contains brief overviews of forecast demand, petroleum geology, petrophysics, formation evaluation, and measurements made while drilling. Several examples show how physics is used to locate and to determine the volume and type of hydrocarbons, the pressure of subsurface fluids, and the formation permeability. Sophisticated instruments built into drill collars measure the subsurface properties at and behind the drill bit. Such measurements include electromagnetic propagation, Compton scattering, neutron scattering, nuclear spectroscopy, and magnetic resonance, among others. The hostile drilling environment (high temperatures, high pressures, and high shock levels) create challenging problems for the physicist and engineer who design such instruments.

  1. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand;

    2015-01-01

    these enzymes may help degrading lignin, using oxygen as the oxidant. Laccases can catalyze polymerization of lignin, but the question is whether and how laccases can directly catalyze modification of lignin via catalytic bond cleavage. Via a thorough review of the available literature and detailed...

  2. Hydrocarbons and energy from plants: Final report, 1984-1987

    Energy Technology Data Exchange (ETDEWEB)

    Calvin, M.; Otvos, J.; Taylor, S.E.; Nemethy, E.K.; Skrukrud, C.L.; Hawkins, D.R.; Lago, R.

    1988-08-01

    Plant hydrocarbon (isoprenoid) production was investigated as an alternative source to fossil fuels. Because of their high triterpenoid (hydrocarbon) content of 4--8%, Euphorbia lathyris plants were used as a model system for this study. The structure of the E. lathyris triterpenoids was determined, and triterpenoid biosynthesis studied to better understand the metabolic regulation of isoprenoid production. Triterpenoid biosynthesis occurs in two distinct tissue types in E. lathyris plants: in the latex of the laticifer cells; and in the mesophyll cells of the leaf and stem. The latex has been fractionated by centrifugation, and it has been determined that the later steps of isoprenoid biosynthesis, the conversion of mevalonic acid to the triterpenes, are compartmentized within a vacuole. Also identified was the conversion of hydroxymethyl glutaryl-CoA to mevalonic acid, catalyzed by the enzyme Hydroxymethyl glutaryl-CoA Reductase, as a key rate limiting step in isoprenoid biosynthesis. At least two isozymes of this enzyme, one in the latex and another in the leaf plastids, have been identified. Environmental stress has been applied to plants to study changes in carbon allocation. Salinity stress caused a large decrease in growth, smaller decreases in photosynthesis, resulting in a larger allocation of carbon to both hydrocarbon and sugar production. An increase in Hydroxymethyl glutaryl-CoA Reductase activity was also observed when isoprenoid production increased. Other species where also screened for the production of hydrogen rich products such as isoprenoids and glycerides, and their hydrocarbon composition was determined.

  3. Superconductivity in aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Kubozono, Yoshihiro, E-mail: kubozono@cc.okayama-u.ac.jp [Research Laboratory for Surface Science, Okayama University, Okayama 700-8530 (Japan); Research Center of New Functional Materials for Energy Production, Storage and Transport, Okayama University, Okayama 700-8530 (Japan); Japan Science and Technology Agency, ACT-C, Kawaguchi 332-0012 (Japan); Goto, Hidenori; Jabuchi, Taihei [Research Laboratory for Surface Science, Okayama University, Okayama 700-8530 (Japan); Yokoya, Takayoshi [Research Laboratory for Surface Science, Okayama University, Okayama 700-8530 (Japan); Research Center of New Functional Materials for Energy Production, Storage and Transport, Okayama University, Okayama 700-8530 (Japan); Kambe, Takashi [Department of Physics, Okayama University, Okayama 700-8530 (Japan); Sakai, Yusuke; Izumi, Masanari; Zheng, Lu; Hamao, Shino; Nguyen, Huyen L.T. [Research Laboratory for Surface Science, Okayama University, Okayama 700-8530 (Japan); Sakata, Masafumi; Kagayama, Tomoko; Shimizu, Katsuya [Center of Science and Technology under Extreme Conditions, Osaka University, Osaka 560-8531 (Japan)

    2015-07-15

    Highlights: • Aromatic superconductor is one of core research subjects in superconductivity. Superconductivity is observed in certain metal-doped aromatic hydrocarbons. Some serious problems to be solved exist for future advancement of the research. This article shows the present status of aromatic superconductors. - Abstract: ‘Aromatic hydrocarbon’ implies an organic molecule that satisfies the (4n + 2) π-electron rule and consists of benzene rings. Doping solid aromatic hydrocarbons with metals provides the superconductivity. The first discovery of such superconductivity was made for K-doped picene (K{sub x}picene, five benzene rings). Its superconducting transition temperatures (T{sub c}’s) were 7 and 18 K. Recently, we found a new superconducting K{sub x}picene phase with a T{sub c} as high as 14 K, so we now know that K{sub x}picene possesses multiple superconducting phases. Besides K{sub x}picene, we discovered new superconductors such as Rb{sub x}picene and Ca{sub x}picene. A most serious problem is that the shielding fraction is ⩽15% for K{sub x}picene and Rb{sub x}picene, and it is often ∼1% for other superconductors. Such low shielding fractions have made it difficult to determine the crystal structures of superconducting phases. Nevertheless, many research groups have expended a great deal of effort to make high quality hydrocarbon superconductors in the five years since the discovery of hydrocarbon superconductivity. At the present stage, superconductivity is observed in certain metal-doped aromatic hydrocarbons (picene, phenanthrene and dibenzopentacene), but the shielding fraction remains stubbornly low. The highest priority research area is to prepare aromatic superconductors with a high superconducting volume-fraction. Despite these difficulties, aromatic superconductivity is still a core research target and presents interesting and potentially breakthrough challenges, such as the positive pressure dependence of T{sub c} that is clearly

  4. Catalyzed electrolytic plutonium oxide dissolution

    International Nuclear Information System (INIS)

    Catalyzed electrolytic plutonium oxide dissolution (CEPOD) was first demonstrated at Pacific Northwest Laboratory (PNL) in early 1974 in work funded by the Exxon Corporation. The work, aimed at dissolution of Pu-containing residues remaining after the dissolution of spent mixed-oxide reactor fuels, was first publicly disclosed in 1981. The process dissolves PuO2 in an anolyte containing small (catalytic) amounts of elements that form kinetically fast, strongly oxidizing ions. These are continuously regenerated at the anode. Catalysts used, in their oxidized form, include Ag2+, Ce4+, Co3+, and AmO22+. This paper reviews the chemistry involved in CEPOD and the results of its application to the dissolution of the Pu content of a variety of PuO2-containing materials such as off-standard oxide, fuels dissolution residues, incinerator ash, contaminated soils, and other scraps or wastes. Results are presented for both laboratory-scale and plant-scale dissolves

  5. Gold-catalyzed naphthalene functionalization

    Directory of Open Access Journals (Sweden)

    Iván Rivilla

    2011-05-01

    Full Text Available The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenylimidazol-2-ylidene, M = Cu, 1a; M = Au, 1b, in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethylphenyl, catalyze the transfer of carbene groups: C(RCO2Et (R = H, Me from N2C(RCO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed.

  6. Cytochrome b5 and epoxide hydrolase contribute to benzo[a]pyrene-DNA adduct formation catalyzed by cytochrome P450 1A1 under low NADPH:P450 oxidoreductase conditions

    International Nuclear Information System (INIS)

    In previous studies we had administered benzo[a]pyrene (BaP) to genetically engineered mice (HRN) which do not express NADPH:cytochrome P450 oxidoreductase (POR) in hepatocytes and observed higher DNA adduct levels in livers of these mice than in wild-type mice. To elucidate the reason for this unexpected finding we have used two different settings for in vitro incubations; hepatic microsomes from control and BaP-pretreated HRN mice and reconstituted systems with cytochrome P450 1A1 (CYP1A1), POR, cytochrome b5, and epoxide hydrolase (mEH) in different ratios. In microsomes from BaP-pretreated mice, in which Cyp1a1 was induced, higher levels of BaP metabolites were formed, mainly of BaP-7,8-dihydrodiol. At a low POR:CYP1A1 ratio of 0.05:1 in the reconstituted system, the amounts of BaP diones and BaP-9-ol formed were essentially the same as at an equimolar ratio, but formation of BaP-3-ol was ∼1.6-fold higher. Only after addition of mEH were BaP dihydrodiols found. Two BaP-DNA adducts were formed in the presence of mEH, but only one when CYP1A1 and POR were present alone. At a ratio of POR:CYP1A1 of 0.05:1, addition of cytochrome b5 increased CYP1A1-mediated BaP oxidation to most of its metabolites indicating that cytochrome b5 participates in the electron transfer from NADPH to CYP1A1 required for enzyme activity of this CYP. BaP-9-ol was formed even by CYP1A1 reconstituted with cytochrome b5 without POR. Our results suggest that in livers of HRN mice Cyp1a1, cytochrome b5 and mEH can effectively activate BaP to DNA binding species, even in the presence of very low amounts of POR

  7. Horseradish peroxidase catalyzed hydroxylations: mechanistic studies.

    Science.gov (United States)

    Dordick, J S; Klibanov, A M; Marletta, M A

    1986-05-20

    The hydroxylation of phenol to hydroquinone and catechol in the presence of dihydroxyfumaric acid and oxygen catalyzed by horseradish peroxidase was studied under conditions where the product yield was high and the side reactions were minimal. The reaction is partially uncoupled with a molar ratio of dihydroxyfumaric acid consumed to hydroxylated products of 12:1. Hydrogen peroxide does not participate in the reaction as evidenced by the lack of effect of catalase and by the direct addition of hydrogen peroxide. Conversely, superoxide and hydroxyl radicals are involved as their scavengers are potent inhibitors. Experiments were all consistent with the involvement of compound III (oxygenated ferrous complex) of peroxidase in the reaction. Compound III is stable in the presence of phenol alone but decomposes rapidly in the presence of both phenol and dihydroxyfumaric acid with the concomitant formation of product. Therefore, phenol and dihydroxyfumaric acid must be present with compound III in order for the hydroxylation reaction to occur. A mechanism consistent with the experimental results is proposed. PMID:3718931

  8. Stereoselective Palladium Catalyzed Cyclizations of Enediyne Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Chang Ho; Rhim, Chul Yun; Jung, Hyung Hoon; Jung, Seung Hyun [Hanyang University, Seoul (Korea, Republic of)

    1999-06-15

    Hydropalladium carboxylates, formed from {pi}-allylpalladium chloride dimer plus carboxylic acids, have been shown to catalyze cyclization of structurally diverse enediynes to form the corresponding six- or five-membered rings depending upon the reaction conditions. Some enediynes having an oxygen linker in an appropriate position under the similar condition yielded the corresponding cyclopropanation products in highly stereoselective manner. A study using deuterated formic acid has proven that the alkylpalladium intermediates formed in our conditions were reduced by the pendant formate ligand. The dienediyne 10 yielded only the tricyclic product 12 in 67% yield, although it was expected to form the cyclic product 11. All these cyclizations seemed to occur via the corresponding alkylpalladium intermediates I, which could proceed to the corresponding cyclic products depending on the reaction conditions and the substrates. The study using deuterated formic acid could provide an important information to understand the present cyclization mechanism. Overall the present study could play an important role in developing new synthetic methodologies for constructing complex polycyclic compounds

  9. Membrane separation of hydrocarbons

    Science.gov (United States)

    Chang, Y. Alice; Kulkarni, Sudhir S.; Funk, Edward W.

    1986-01-01

    Mixtures of heavy oils and light hydrocarbons may be separated by passing the mixture through a polymeric membrane. The membrane which is utilized to effect the separation comprises a polymer which is capable of maintaining its integrity in the presence of hydrocarbon compounds and which has been modified by being subjected to the action of a sulfonating agent. Sulfonating agents which may be employed will include fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, etc., the surface or bulk modified polymer will contain a degree of sulfonation ranging from about 15 to about 50%. The separation process is effected at temperatures ranging from about ambient to about 100.degree. C. and pressures ranging from about 50 to about 1000 psig.

  10. 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.

  11. 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

  12. Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

    Science.gov (United States)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

    2012-01-01

    We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

  13. Horseradish peroxidase-catalyzed polymerization of cardanol in the presence of redox mediators.

    Science.gov (United States)

    Won, Keehoon; Kim, Yong Hwan; An, Eun Suk; Lee, Yeon Soo; Song, Bong Keun

    2004-01-01

    Horseradish peroxidase-catalyzed polymerization of cardanol in aqueous organic solvent was investigated in the presence of a redox mediator. Cardanol is a phenol derivative from a renewable resource mainly having a C15 unsaturated hydrocarbon chain with mostly 1-3 double bonds at a meta position. Unlike soybean peroxidase (SBP), it has been shown that horseradish peroxidase (HRP) is not able to perform oxidative polymerization of phenol derivatives having a bulky meta substituent such as cardanol. For the first time, redox mediators have been applied to enable horseradish peroxidase to polymerize cardanol. Veratryl alcohol, N-ethyl phenothiazine, and phenothiazine-10-propionic acid were tested as a mediator. It is surprising that the horseradish peroxidase-catalyzed polymerization of cardanol took place in the presence of N-ethyl phenothiazine or phenothiazine-10-propionic acid. However, veratryl alcohol showed no effect. FT-IR and GPC analysis of the product revealed that the structure and properties of polycardanol formed by HRP with a mediator were similar to those by SBP. This is the first work to apply a redox mediator to enzyme-catalyzed oxidative polymerization. Our new finding that oxidative polymerization of a poor substrate, which the enzyme is not active with, can take place in the presence of an appropriate mediator will present more opportunities for the application of enzyme-catalyzed polymerization. PMID:14715000

  14. Macroporous polymer foams by hydrocarbon templating.

    Science.gov (United States)

    Shastri, V P; Martin, I; Langer, R

    2000-02-29

    Porous polymeric media (polymer foams) are utilized in a wide range of applications, such as thermal and mechanical insulators, solid supports for catalysis, and medical devices. A process for the production of polymer foams has been developed. This process, which is applicable to a wide range of polymers, uses a hydrocarbon particulate phase as a template for the precipitation of the polymer phase and subsequent pore formation. The use of a hydrocarbon template allows for enhanced control over pore structure, porosity, and other structural and bulk characteristics of the polymer foam. Polymer foams with densities as low as 120 mg/cc, porosity as high as 87%, and high surface areas (20 m(2)/g) have been produced. Foams of poly(l-lactic acid), a biodegradable polymer, produced by this process have been used to engineer a variety of different structures, including tissues with complex geometries such as in the likeness of a human nose. PMID:10696111

  15. The presence of hydrocarbons in southeast Norway

    DEFF Research Database (Denmark)

    Hanken, Niels Martin; Hansen, Malene Dolberg; Kresten Nielsen, Jesper;

    pyrobitumen occurs as a jet-black, brittle, amorphous, non-fluorescent substance with a specific gravity of about 1.3 g/cm3 and a conchoidal fracture. Earlier analyses have shown great similarities with regard to the stable isotopes d13C in Alum Shale (Middle Cambrian to Lower Ordovician) and pyrobitumen......, indicating that Alum Shale was the most important source rock. Petrographic investigations combined with stable isotope analyses (d13C and d18O) of the cement containing pyrobitumen indicate two phases of hydrocarbon migration. The first phase probably took place in Upper Silurian to Lower Devonian time......, when the Alum Shale entered the oil window. These hydrocarbons are mostly found as pyrobitumen in primary voids and calcite cemented veins in Cambro-Silurian sedimentary deposits. The second phase is probably of Late Carboniferous/Permian age and was due to the increased heat flow during the formation...

  16. Nanoparticulate-catalyzed oxygen transfer processes

    Science.gov (United States)

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

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

  17. Relevance and Significance of Extraterrestrial Abiological Hydrocarbon Chemistry.

    Science.gov (United States)

    Olah, George A; Mathew, Thomas; Prakash, G K Surya

    2016-06-01

    Astrophysical observations show similarity of observed abiological "organics"-i.e., hydrocarbons, their derivatives, and ions (carbocations and carbanions)-with studied terrestrial chemistry. Their formation pathways, their related extraterrestrial hydrocarbon chemistry originating from carbon and other elements after the Big Bang, their parent hydrocarbon and derivative (methane and methanol, respectively), and transportation of derived building blocks of life by meteorites or comets to planet Earth are discussed in this Perspective. Their subsequent evolution on Earth under favorable "Goldilocks" conditions led to more complex molecules and biological systems, and eventually to humans. The relevance and significance of extraterrestrial hydrocarbon chemistry to the limits of science in relation to the physical aspects of evolution on our planet Earth are also discussed. PMID:27045758

  18. Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

    OpenAIRE

    Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F.

    2014-01-01

    Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminat...

  19. Update on muon-catalyzed fusion research at LAMPF

    International Nuclear Information System (INIS)

    An experimental investigation of muon-catalyzed fusion in mixtures of the hydrogen isotopes (and helium) began in 1982 at the Los Alamos Meson Physics Facility. The explorations cover a wide range of mixture densities (12 to 140% liquid hydrogen density) and temperatures (13 to 1800K). Many parameters of muon catalysis have been measured for the first time, including distinct dtμ-molecular formation rates as functions of temperature and density. The discovery that the effective α-μ sticking probability becomes quite small for elevated mixture densities is particularly intriguing and challenging to our understanding. Preliminary new results will be presented in the context of acquired results

  20. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    The viability of a symbiotic combination of Muon Catalyzed Fusion (μCF) and high density generation processes has been investigated. The muon catalyzed fusion reaction rates are formulated in the temperature and density range found under moderate compressive conditions. Simplified energy gain and power balance calculations indicate that significant energy gain occurs only if standard type deuterium-tritium (dt) fusion is ignited. A computer simulation of the hydrodynamics and fusion kinetics of a spherical deuterium-tritium pellet implosion including muons is performed. Using the muon catalyzed fusion reaction rates formulated and under ideal conditions, the pellet ignites (and thus has a significant energy gain) only if the initial muon concentration is approximately 1017 cm-3. The muons need to be delivered to the pellet within a very short-time (≅ 1 ns). The muon pulse required in order to make the high density and temperature muon catalyzed fusion scheme viable is beyond the present technology for muon production. (orig.)

  1. LEWIS ACID CATALYZED FORMATION OF TETRAHYDROPYRANS IN IONIC LIQUID

    Science.gov (United States)

    Tetrahydropyrans are integral moieties in innumerable natural products and have inspired the development of a variety of different methodologies. A Prins-type cyclization involving the coupling of a homoallylic alcohol and an aldehyde in the presence of catalytic scandium triflat...

  2. Palladium-Catalyzed Carbonylation and Arylation Reactions

    OpenAIRE

    Sävmarker, Jonas

    2012-01-01

    Palladium-catalyzed reactions have found widespread use in contemporary organic chemistry due to their impressive range of functional group tolerance and high chemo- and regioselectivity. The pioneering contributions to the development of the Pd-catalyzed C-C bond forming cross-coupling reaction were rewarded with the Nobel Prize in Chemistry in 2010. Today, this is a rapidly growing field, and the development of novel methods, as well as the theoretical understanding of the various processes...

  3. A new manganese-mediated, cobalt-catalyzed three-component synthesis of (diarylmethylsulfonamides

    Directory of Open Access Journals (Sweden)

    Antoine Pignon

    2014-02-01

    Full Text Available The synthesis of (diarylmethylsulfonamides and related compounds by a new manganese-mediated, cobalt-catalyzed three-component reaction between sulfonamides, carbonyl compounds and organic bromides is described. This organometallic Mannich-like process allows the formation of the coupling products within minutes at room temperature. A possible mechanism, emphasizing the crucial role of manganese is proposed.

  4. GSTP1-1 stereospecifically catalyzes glutathione conjugation of ethacrynic acid

    NARCIS (Netherlands)

    Iersel, M.L.P.S. van; Lipzig, M.M.H. van; Rietjens, I.M.C.M.; Vervoort, J.; Bladeren, P.J. van

    1998-01-01

    Using 1H NMR two diastereoisomers of the ethacrynic acid glutathione conjugate (EASG) as well as ethacrynic acid (EA) could be distinguished and quantified individually. Chemically prepared EASG consists of equal amounts of both diastereoisomers. GSTP1-1 stereospecifically catalyzes formation of one

  5. A new manganese-mediated, cobalt-catalyzed three-component synthesis of (diarylmethyl)sulfonamides

    Science.gov (United States)

    Pignon, Antoine; Martens, Thierry

    2014-01-01

    Summary The synthesis of (diarylmethyl)sulfonamides and related compounds by a new manganese-mediated, cobalt-catalyzed three-component reaction between sulfonamides, carbonyl compounds and organic bromides is described. This organometallic Mannich-like process allows the formation of the coupling products within minutes at room temperature. A possible mechanism, emphasizing the crucial role of manganese is proposed. PMID:24605162

  6. Clauson Kaas Pyrrole Synthesis Catalyzed by Acidic Ionic Liquid under Microwave Irradiation

    OpenAIRE

    Cigdem Yolacan; Feray Aydogan

    2013-01-01

    A new procedure to synthesize the N-substituted pyrrole derivatives by Clauson Kaas reaction catalyzed by acidic ionic liquid under microwave irradiation was developed. This procedure provides several advantages such as high yield, clean product formation, and short reaction time.

  7. DFT Investigation of the Palladium-Catalyzed Ene-Yne Coupling

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Tanner, David Ackland; Skrydstrup, T.;

    2010-01-01

    The mechanism of the recently developed palladium-catalyzed ene-yne coupling has been evaluated by DFT methods. The calculations validate the previously proposed reaction mechanism and explain the stereoselectivity of the reaction (exclusive formation of the E isomer of the disubstituted alkene)....

  8. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. IV. Chemical dynamics of methylpropargyl radical formation, C{sub 4}H{sub 5}, from reaction of C({sup 3}P{sub j}) with propylene, C{sub 3}H{sub 6} (X{sup 1}A)

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, R.I.; Stranges, D.; Bevsek, H.M.; Lee, Y.T.; Suits, A.G. [Department of Chemistry, University of California, Berkeley, California 94720 (United States)]|[Chemical Sciences Division, Berkeley National Laboratory, Berkeley, California 94720 (United States)

    1997-03-01

    The reaction between ground state carbon atoms and propylene, C{sub 3}H{sub 6}, was studied at average collision energies of 23.3 and 45.0 kJmol{sup {minus}1} using the crossed molecular beam technique. Product angular distributions and time-of-flight spectra of C{sub 4}H{sub 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 {sup 3}A surface via an initial addition of the carbon atom to the {pi}-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{sub 4}H{sub 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} {ital 1997 American Institute of Physics.}

  9. Chemical characteristics of Jurassic formation water and its relationship with hydrocarbon migration and accumulation in middle part of Western Sichuan Depression%川西坳陷中段侏罗系次生气藏地层水化学特征及与油气运聚关系

    Institute of Scientific and Technical Information of China (English)

    叶素娟; 李嵘; 张世华

    2014-01-01

    川西坳陷侏罗系地层水化学研究结果表明,侏罗系地层水以CaCl2型为主,其中上侏罗统蓬莱镇组见较多Na2 SO4型地层水,结合地层水离子参数,总体上地层水封闭条件较好,有利于油气的聚集和保存。侏罗系地层水化学特征在垂向和平面上表现出明显的垂直分带性和平面分区性。纵向上,侏罗系地层水总体表现出断层越流淡化地层水的特征;平面上,地层水矿化度、主要离子浓度受构造位置以及断裂系统控制。构造位置较高或邻近烃源断层的地区,侏罗系地层水受大气水下渗淡化作用和须家河组五段湖相泥岩黏土矿物脱水淡化作用影响。与中国大部分油气田不同,川西坳陷侏罗系次生气藏主要分布在矿化度小于30 g/L,HCO-3浓度大于300 mg/L的区域。须家河组五段烃源岩黏土矿物转化析出的大量低矿化度层间水与有机质热演化和硫酸盐还原作用形成的烃类和CO2气体,在断层沟通下上涌进入侏罗系储层,导致低矿化度、高HCO-3浓度地层水的分布范围与气藏分布有较好的一致性。在断层欠发育地区,地层垂向连通性差,侏罗系次生气藏难以形成,地层水具有较高的矿化度和较低的HCO-3浓度。%Studies on the chemistry of the Jurassic formation water indicate that the formation water is dominantly characterized by CaCl2 type with relatively low salinity and Na2SO4 type water is common in the Upper Jurassic Penglaizhen Formation. In general, the Jurassic formation water is in a closed system, demonstrating its favorableness for hydrocarbon accumulation and preservation. There is a distinct difference in the chemistry of formation water verti-cally and horizontally. Water composition varies with depth and three vertical variation patterns might be observed, showing the diluting effect caused by the cross-formation flow through faults. Regionally, formation water chemistry

  10. Creating and maintaining a gas cap in tar sands formations

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX); Karanikas, John Michael (Houston, TX); Dinkoruk, Deniz Sumnu (Houston, TX); Wellington, Scott Lee (Bellaire, TX)

    2010-03-16

    Methods for treating a tar sands formation are disclosed herein. Methods for treating a tar sands formation may include providing heat to at least part of a hydrocarbon layer in the formation from one or more heaters located in the formation. Pressure may be allowed to increase in an upper portion of the formation to provide a gas cap in the upper portion. At least some hydrocarbons are produced from a lower portion of the formation.

  11. Structure and Hydrocarbons in Junggar Basin

    Institute of Scientific and Technical Information of China (English)

    张庆春; 田在艺

    2002-01-01

    Having undergone four basin-forming tectonic cycles--Hercynian, Indosinian, Yanshanian, and Himalayan, the Junggar basin becomes a multi-cyclic superposed basin of old and hard mediun block pattern. Its multi-cyclic tectonic and sedimentary evolution results in five series of hydrocarbon source rock formations--Carboniferous, Permian, Upper Triassic, Middle-lower Jurassic, and Lower Tertiary, correspondingly forming five petroleum generation systems, of which the Permian and Middle-lower Jurassic petroleum generation systems are the most important with the highest exploration degree. Hydrocarbons are controlled by basin structure as follows: 1) Hydrocarbon accumulations are controlled by the structural styles of paleo-uplifts, paleo-overthrust belts and contorted anticline belts formed in multi-cyclic tectonic movements; 2) Important pathways for long distance lateral and vertical migration are provided respectively by unconformities and faults; 3) The pool-forming characteristics of the Permian petroleum system are controlled by paleo-structure; 4) The pool-forming characteristics of Jurassic and Tertiary petroleum system are controlled by recent structures.

  12. Adsorption of hydrocarbons in chalk reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Madsen, L.

    1996-12-31

    The present work is a study on the wettability of hydrocarbon bearing chalk reservoirs. Wettability is a major factor that influences flow, location and distribution of oil and water in the reservoir. The wettability of the hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. Organic compounds such as carboxylic acids are found in formation waters from various hydrocarbon reservoirs and in crude oils. In the present investigation the wetting behaviour of chalk is studied by the adsorption of the carboxylic acids onto synthetic calcite, kaolinite, quartz, {alpha}-alumina, and chalk dispersed in an aqueous phase and an organic phase. In the aqueous phase the results clearly demonstrate the differences between the adsorption behaviour of benzoic acid and hexanoic acid onto the surfaces of oxide minerals and carbonates. With NaCl concentration of 0.1 M and with pH {approx_equal} 6 the maximum adsorption of benzoic acid decreases in the order: quartz, {alpha}-alumina, kaolinite. For synthetic calcite and chalk no detectable adsorption was obtaind. In the organic phase the order is reversed. The maximum adsorption of benzoic acid onto the different surfaces decreases in the order: synthetic calcite, chalk, kaolinite and quartz. Also a marked difference in adsorption behaviour between probes with different functional groups onto synthetic calcite from organic phase is observed. The maximum adsorption decreases in the order: benzoic acid, benzyl alcohol and benzylamine. (au) 54 refs.

  13. Thermophysical Properties of Hydrocarbon Mixtures

    Science.gov (United States)

    SRD 4 NIST Thermophysical Properties of Hydrocarbon Mixtures (PC database for purchase)   Interactive computer program for predicting thermodynamic and transport properties of pure fluids and fluid mixtures containing up to 20 components. The components are selected from a database of 196 components, mostly hydrocarbons.

  14. Volatile Hydrocarbon Pheromones from Beetles

    Science.gov (United States)

    This chapter reviews literature about hydrocarbons from beetles that serve as long-range pheromones. The most thoroughly studied beetles that use volatile hydrocarbon pheromones belong to the family Nitidulidae in the genera Carpophilus and Colopterus. Published pheromone research deals with behav...

  15. Biodegradation aspects of Polycyclic Aromatic Hydrocarbons (PAHs): A review

    International Nuclear Information System (INIS)

    PAHs are aromatic hydrocarbons with two or more fused benzene rings with natural as well as anthropogenic sources. They are widely distributed environmental contaminants that have detrimental biological effects, toxicity, mutagenecity and carcinogenicity. Due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity, the PAHs have gathered significant environmental concern. Although PAH may undergo adsorption, volatilization, photolysis, and chemical degradation, microbial degradation is the major degradation process. PAH degradation depends on the environmental conditions, number and type of the microorganisms, nature and chemical structure of the chemical compound being degraded. They are biodegraded/biotransformed into less complex metabolites, and through mineralization into inorganic minerals, H2O, CO2 (aerobic) or CH4 (anaerobic) and rate of biodegradation depends on pH, temperature, oxygen, microbial population, degree of acclimation, accessibility of nutrients, chemical structure of the compound, cellular transport properties, and chemical partitioning in growth medium. A number of bacterial species are known to degrade PAHs and most of them are isolated from contaminated soil or sediments. Pseudomonas aeruginosa, Pseudomons fluoresens, Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Lignolytic fungi too have the property of PAH degradation. Phanerochaete chrysosporium, Bjerkandera adusta, and Pleurotus ostreatus are the common PAH-degrading fungi. Enzymes involved in the degradation of PAHs are oxygenase, dehydrogenase and lignolytic enzymes. Fungal lignolytic enzymes are lignin peroxidase, laccase, and manganese peroxidase. They are extracellular and catalyze radical formation by oxidation to destabilize bonds in a molecule. The biodegradation of PAHs has been observed under both aerobic and anaerobic conditions and the rate can be

  16. Biodegradation aspects of Polycyclic Aromatic Hydrocarbons (PAHs): A review

    Energy Technology Data Exchange (ETDEWEB)

    Haritash, A.K., E-mail: akharitash@gmail.com [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar, Haryana (India); Kaushik, C.P. [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar, Haryana (India)

    2009-09-30

    PAHs are aromatic hydrocarbons with two or more fused benzene rings with natural as well as anthropogenic sources. They are widely distributed environmental contaminants that have detrimental biological effects, toxicity, mutagenecity and carcinogenicity. Due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity, the PAHs have gathered significant environmental concern. Although PAH may undergo adsorption, volatilization, photolysis, and chemical degradation, microbial degradation is the major degradation process. PAH degradation depends on the environmental conditions, number and type of the microorganisms, nature and chemical structure of the chemical compound being degraded. They are biodegraded/biotransformed into less complex metabolites, and through mineralization into inorganic minerals, H{sub 2}O, CO{sub 2} (aerobic) or CH{sub 4} (anaerobic) and rate of biodegradation depends on pH, temperature, oxygen, microbial population, degree of acclimation, accessibility of nutrients, chemical structure of the compound, cellular transport properties, and chemical partitioning in growth medium. A number of bacterial species are known to degrade PAHs and most of them are isolated from contaminated soil or sediments. Pseudomonas aeruginosa, Pseudomons fluoresens, Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Lignolytic fungi too have the property of PAH degradation. Phanerochaete chrysosporium, Bjerkandera adusta, and Pleurotus ostreatus are the common PAH-degrading fungi. Enzymes involved in the degradation of PAHs are oxygenase, dehydrogenase and lignolytic enzymes. Fungal lignolytic enzymes are lignin peroxidase, laccase, and manganese peroxidase. They are extracellular and catalyze radical formation by oxidation to destabilize bonds in a molecule. The biodegradation of PAHs has been observed under both aerobic and anaerobic conditions

  17. Hydrocarbon Migration and Accumulation in Dongying Basin

    Institute of Scientific and Technical Information of China (English)

    Li Chunguang; Shang Weirong

    1996-01-01

    @@ Dongying basin is a faulted basin rich in hydrocarbon and is under more exploration (wildcat well density is 0.155 well/km ) in the southern Bohai Bay area of China, covering an area of 5700 km. Based on the paleotopographic setting of Paleozoic basement rocks, the basin was evolved into Mesozoic and Cenozoic basin which was faulted in the north and overlapped in the south by the blockfaulting movement in J2-J3. So, each formation of the source rocks in Paleogene is characterized by thick deposit in the north and thin deposit in the south.

  18. Diterpenoid tetracyclic hydrocarbons of petroleum

    Energy Technology Data Exchange (ETDEWEB)

    Vorob' eva, N.S.; Zemskova, Z.K.; Pekh, T.I.; Petrov, A.A.

    1987-08-01

    Diterpenoid hydrocarbons are fairly widespread in various caustobioliths. However, if petroleums contain mainly acyclic diterpenoids (phytane, pristane and norpristane), cyclic diterpaenes such as fichtelite, pimarane, iosene (kaurane) and hibbane are often found in hydrocarbons isolated from coal and shale. Recent advances in the chemistry of diterpenoids isolated from caustobioliths, are described in a separate paper. Much less is known about petroleum polycyclic diterpenoid hydrocarbons, particularly those with four saturated rings. A series of tetracyclic hydrocarbons C/sub 19/H/sub 32/ (molar mass 260), found in a number of light petroleums and gas condensates from the Jura deposits of Central Kara-Kum (Turkmen S.S.R.), are examined here. These hydrocarbons are present in petroleums and condensates from the Davaly, Erden, Ortakak, Southern Beuideshik deposits, they are always identical and occur in the same ratios. The composition of the tretracyclanes isolated from the Ortakak gas condensates (well 17) will be examined in detail.

  19. Hydrocarbon sensors and materials therefor

    Science.gov (United States)

    Pham, Ai Quoc; Glass, Robert S.

    2000-01-01

    An electrochemical hydrocarbon sensor and materials for use in sensors. A suitable proton conducting electrolyte and catalytic materials have been found for specific application in the detection and measurement of non-methane hydrocarbons. The sensor comprises a proton conducting electrolyte sandwiched between two electrodes. At least one of the electrodes is covered with a hydrocarbon decomposition catalyst. Two different modes of operation for the hydrocarbon sensors can be used: equilibrium versus non-equilibrium measurements and differential catalytic. The sensor has particular application for on-board monitoring of automobile exhaust gases to evaluate the performance of catalytic converters. In addition, the sensor can be utilized in monitoring any process where hydrocarbons are exhausted, for instance, industrial power plants. The sensor is low cost, rugged, sensitive, simple to fabricate, miniature, and does not suffer cross sensitivities.

  20. Thermocatalytic CO2-Free Production of Hydrogen from Hydrocarbon Fuels

    Energy Technology Data Exchange (ETDEWEB)

    University of Central Florida

    2004-01-30

    The main objective of this project is the development of an economically viable thermocatalytic process for production of hydrogen and carbon from natural gas or other hydrocarbon fuels with minimal environmental impact. The three major technical goals of this project are: (1) to accomplish efficient production of hydrogen and carbon via sustainable catalytic decomposition of methane or other hydrocarbons using inexpensive and durable carbon catalysts, (2) to obviate the concurrent production of CO/CO{sub 2} byproducts and drastically reduce CO{sub 2} emissions from the process, and (3) to produce valuable carbon products in order to reduce the cost of hydrogen production The important feature of the process is that the reaction is catalyzed by carbon particulates produced in the process, so no external catalyst is required (except for the start-up operation). This results in the following advantages: (1) no CO/CO{sub 2} byproducts are generated during hydrocarbon decomposition stage, (2) no expensive catalysts are used in the process, (3) several valuable forms of carbon can be produced in the process depending on the process conditions (e.g., turbostratic carbon, pyrolytic graphite, spherical carbon particles, carbon filaments etc.), and (4) CO{sub 2} emissions could be drastically reduced (compared to conventional processes).

  1. Geophysical monitoring in a hydrocarbon reservoir

    Science.gov (United States)

    Caffagni, Enrico; Bokelmann, Goetz

    2016-04-01

    Extraction of hydrocarbons from reservoirs demands ever-increasing technological effort, and there is need for geophysical monitoring to better understand phenomena occurring within the reservoir. Significant deformation processes happen when man-made stimulation is performed, in combination with effects deriving from the existing natural conditions such as stress regime in situ or pre-existing fracturing. Keeping track of such changes in the reservoir is important, on one hand for improving recovery of hydrocarbons, and on the other hand to assure a safe and proper mode of operation. Monitoring becomes particularly important when hydraulic-fracturing (HF) is used, especially in the form of the much-discussed "fracking". HF is a sophisticated technique that is widely applied in low-porosity geological formations to enhance the production of natural hydrocarbons. In principle, similar HF techniques have been applied in Europe for a long time in conventional reservoirs, and they will probably be intensified in the near future; this suggests an increasing demand in technological development, also for updating and adapting the existing monitoring techniques in applied geophysics. We review currently available geophysical techniques for reservoir monitoring, which appear in the different fields of analysis in reservoirs. First, the properties of the hydrocarbon reservoir are identified; here we consider geophysical monitoring exclusively. The second step is to define the quantities that can be monitored, associated to the properties. We then describe the geophysical monitoring techniques including the oldest ones, namely those in practical usage from 40-50 years ago, and the most recent developments in technology, within distinct groups, according to the application field of analysis in reservoir. This work is performed as part of the FracRisk consortium (www.fracrisk.eu); this project, funded by the Horizon2020 research programme, aims at helping minimize the

  2. Hydrocarbon saturation determination using acoustic velocities obtained through casing

    Science.gov (United States)

    Moos, Daniel

    2010-03-09

    Compressional and shear velocities of earth formations are measured through casing. The determined compressional and shear velocities are used in a two component mixing model to provides improved quantitative values for the solid, the dry frame, and the pore compressibility. These are used in determination of hydrocarbon saturation.

  3. An Iridium-Catalyzed Reductive Approach to Nitrones from N-Hydroxyamides.

    Science.gov (United States)

    Katahara, Seiya; Kobayashi, Shoichiro; Fujita, Kanami; Matsumoto, Tsutomu; Sato, Takaaki; Chida, Noritaka

    2016-04-27

    An Ir-catalyzed reductive formation of functionalized nitrones from N-hydroxyamides was reported. The reaction took place through two types of iridium-catalyzed reactions including dehydrosilylation and hydrosilylation. The method showed high chemoselectivity in the presence of sensitive functional groups, such as methyl esters, and was successfully applied to the synthesis of cyclic and macrocyclic nitrones, which are known to be challenging compounds to access by conventional methods. (1)H NMR studies strongly supported generation of an N-siloxyamide and an N,O-acetal as the actual intermediates. PMID:27071479

  4. Synthesis of benzofuranyl and indolyl methyl azides by tandem silver-catalyzed cyclization and azidation.

    Science.gov (United States)

    Ranjith Kumar, Gadi; Kiran Kumar, Yalla; Kant, Ruchir; Sridhar Reddy, Maddi

    2016-04-26

    Ag(i)-catalyzed synthesis of 2-azidomethyl benzofurans/indoles from linear and readily available hydroxyl/amino-phenyl propargyl alcohols is described via a highly regioselective C-O and C-N bond formation. Control experiments reveal that the reaction involves the sequential Ag(i)-catalyzed 5-exo-dig cyclization and a catalyst free γ-allylic azidation. The synthetic utility of this method has been demonstrated by using the azidomethyl unit of the above synthesized heterocycles as the base for a variety of other functionalizations, such as triazole-, tetrazole-, amide-, amine-, and pyrido-derivatives. PMID:27064507

  5. Copper-Catalyzed Coupling of Oxime Acetates with Isothiocyanates: A Strategy for 2-Aminothiazoles.

    Science.gov (United States)

    Tang, Xiaodong; Zhu, Zhongzhi; Qi, Chaorong; Wu, Wanqing; Jiang, Huanfeng

    2016-01-15

    A new strategy for 2-aminothiazoles is developed via the copper-catalyzed coupling of oxime acetates with isothiocyanates. Various 4-substituted and 4,5-disubstituted 2-aminothiazoles were formed smoothly under mild reaction conditions. This process involved copper-catalyzed N-O bond cleavage, activation of vinyl sp(2) C-H bonds, and C-S/C-N bond formations. It is noteworthy that the oxime acetates were used not only as a substrate but also as a single oxidant. PMID:26729578

  6. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    OpenAIRE

    Zachary L. Palchak; Nguyen, Paula T; Larsen, Catharine H

    2015-01-01

    Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this unc...

  7. Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil

    Science.gov (United States)

    The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed ...

  8. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene.

    Science.gov (United States)

    Xu, Songchen; Boschen, Jeffery S; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L; Sadow, Aaron D

    2015-09-28

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ(3)-N,Si,C-PhB(Ox(Me2))(Ox(Me2)SiHPh)Im(Mes)}Rh(H)CO][HB(C6F5)3] (, Ox(Me2) = 4,4-dimethyl-2-oxazoline; Im(Mes) = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox(Me2))2Im(Mes)}RhH(SiH2Ph)CO () and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox(Me2))2Im(Mes)}RhH(SiHPh)CO][HB(C6F5)3] generated by H abstraction. Complex catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C6F5)3 catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH3 as the reducing agent. PMID:26278517

  9. From cold to hot: post Hirnantian sedimentary basins in Bolivia- a source rock for hydrocarbon deposits in the Andes? – A case study of the Cancañiri formation

    OpenAIRE

    Mehus, Trine

    2013-01-01

    This thesis introduces to sedimentary rocks sampled in Bolivia, in the Eastern Cordillera. Samples were taken from two different outcrops of the Late Ordovician to Early Silurian Cancañiri Formation, and the comparison of these two localities will be drawn in the results. These rocks have been studied using petrography, geochemistry analysis, TOC, heavy minerals using SEM and CL detector analysis, to reveal the shape, composition and interesting features of the rocks. The Cancañiri Formation ...

  10. Zeolite deactivation during hydrocarbon reactions: characterisation of coke precursors and acidity, product distribution

    OpenAIRE

    Wang, B.

    2008-01-01

    The catalytic conversion of hydrocarbons over zeolites has been applied in large scale petroleum-refining processes. However, there is always formation and retention of heavy by-products, called coke, which causes catalyst deactivation. This deactivation is due to the poisoning of the acid sites and/or pore blockage. The formation of coke on hydrocarbon processing catalysts is of considerable technological and economic importance and a great deal of work has been carried out to this study. Th...

  11. Access to Isoquinolines and Isoquinolin-3-ols via Rh(III)-Catalyzed Coupling/Cyclization Cascade Reaction of Arylimidates and Diazo Compounds.

    Science.gov (United States)

    Li, Xing Guang; Sun, Min; Jin, Qiao; Liu, Kai; Liu, Pei Nian

    2016-05-01

    A Rh(III)-catalyzed coupling/cyclization cascade reaction is described, which involves arylimidates and diazo compounds and proceeds via intermolecular C-C bond formation and subsequent intramolecular C-N bond formation. Mechanistic investigation revealed that the reaction is a two-step process: the initial Rh(III)-catalyzed coupling/cyclization proceeds very fast and the following dehydration is rather slow. The reaction provides a direct approach to isoquinolines and isoquinolin-3-ols without any oxidants. PMID:27042947

  12. Iron-Catalyzed C-C Cross-Couplings Using Organometallics.

    Science.gov (United States)

    Guérinot, Amandine; Cossy, Janine

    2016-08-01

    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed. PMID:27573401

  13. In situ heat treatment from multiple layers of a tar sands formation

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX)

    2010-11-30

    A method for treating a tar sands formation is disclosed. The method includes providing a drive fluid to a first hydrocarbon containing layer of the formation to mobilize at least some hydrocarbons in the first layer. At least some of the mobilized hydrocarbons are allowed to flow into a second hydrocarbon containing layer of the formation. Heat is provided to the second layer from one or more heaters located in the second layer. At least some hydrocarbons are produced from the second layer of the formation.

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

    Science.gov (United States)

    Roes, Augustinus Wilhelmus Maria; Mo, Weijian; Muylle, Michel Serge Marie; Mandema, Remco Hugo; Nair, Vijay

    2009-09-01

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

  15. Synergetic catalysis in hydrocarbon generation

    Energy Technology Data Exchange (ETDEWEB)

    Sabate, R.W. [San`Doil Exploration L.C., New Orleans, LA (United States); Baker, C.C. [Consulting Petroleum Geologist, Metairie, LA (United States)

    1994-12-31

    Thermogenesis as the sole origin of hydrocarbons has been questioned by Gulf Coast geologists for two reasons: (1) lack of thermally mature source beds except on the basin`s Mesozoic rim and (2) persuasive empirical evidence of shallow, early generation, migration, and emplacement. Enigmatically, even subsequent deeper burial of the reservoirs has not resulted in thermal maturity. However, recent laboratory research has identified several natural catalysts that significantly lower temperatures needed for conversion of organic materials into hydrocarbons. Perhaps synergism among these or as-yet-undiscovered catalysts, together with geologic reaction times, is capable of producing hydrocarbons at temperatures low enough for early emplacement.

  16. Synergetic catalysis in hydrocarbon generation

    Energy Technology Data Exchange (ETDEWEB)

    Sabate, R.W. [San`Doil Exploration L.C., New Orleans, LA (United States); Baker, C.C. [NAC of FINDING, Slidell, LA (United States)

    1994-09-01

    Thermogenesis as the sole origin of hydrocarbons has been questioned by Gulf Coast petroleum geologists for two reasons: (1) lack of thermally mature source beds except on the basin`s Mesozoic rim and (2) persuasive empirical evidence of shallow, early migration and emplacement. Enigmatically, even subsequent deeper burial of the reservoirs has not resulted in thermal maturity. However, recent laboratory research has identified several natural catalysts that significantly lower temperatures needed for conversion of organic materials into hydrocarbons. Perhaps synergism among these or as yet undiscovered catalysts, together with geologic reaction times, is capable of producing hydrocarbons at temperatures low enough for early emplacement.

  17. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.

    Science.gov (United States)

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A

    2016-07-13

    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  18. Downhole fluid injection systems, CO2 sequestration methods, and hydrocarbon material recovery methods

    Science.gov (United States)

    Schaef, Herbert T.; McGrail, B. Peter

    2015-07-28

    Downhole fluid injection systems are provided that can include a first well extending into a geological formation, and a fluid injector assembly located within the well. The fluid injector assembly can be configured to inject a liquid CO2/H2O-emulsion into the surrounding geological formation. CO2 sequestration methods are provided that can include exposing a geological formation to a liquid CO2/H2O-emulsion to sequester at least a portion of the CO2 from the emulsion within the formation. Hydrocarbon material recovery methods are provided that can include exposing a liquid CO2/H2O-emulsion to a geological formation having the hydrocarbon material therein. The methods can include recovering at least a portion of the hydrocarbon material from the formation.

  19. Downhole fluid injection systems, CO2 sequestration methods, and hydrocarbon material recovery methods

    Energy Technology Data Exchange (ETDEWEB)

    Schaef, Herbert T.; McGrail, B. Peter

    2015-07-28

    Downhole fluid injection systems are provided that can include a first well extending into a geological formation, and a fluid injector assembly located within the well. The fluid injector assembly can be configured to inject a liquid CO2/H2O-emulsion into the surrounding geological formation. CO2 sequestration methods are provided that can include exposing a geological formation to a liquid CO2/H2O-emulsion to sequester at least a portion of the CO2 from the emulsion within the formation. Hydrocarbon material recovery methods are provided that can include exposing a liquid CO2/H2O-emulsion to a geological formation having the hydrocarbon material therein. The methods can include recovering at least a portion of the hydrocarbon material from the formation.

  20. Attractor Explosions and Catalyzed Vacuum Decay

    Energy Technology Data Exchange (ETDEWEB)

    Green, Daniel; Silverstein, Eva; Starr, David

    2006-05-05

    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new endpoint for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  1. Palladium-Catalyzed Amination of Bromoanthancene

    Institute of Scientific and Technical Information of China (English)

    YU Ming-Xin; CHEN Xiao-Hang; CHENG Chien-Hong

    2003-01-01

    @@ Triarylamines are an important class of compounds, because they have been used as the hole-transport layer in electroluminescent devices. [1] New palladium catalyzed methods to form arylamines have emerged recently from Hartwing and Bucchwald . [2,3] Our group have investigated unusual diboration of allenes catalyzed by palladium complex and organic iodides. [4] Here we will report that arylamines react with bromoanthrancene (or dibromoanthancene) to afford triarylamines in the presence of Ligand-palladium complex. The structures of products were de termined by 1H NMR, 13C NMR, 13C (DEPT), IR and MS (HREI and EI) spectra.

  2. Proceedings of hydrocarbon contaminated soils and groundwater

    International Nuclear Information System (INIS)

    This book reports on hydrogen contaminated soils and groundwater. Topics covered include: perspectives on hydrocarbon contamination; emerging hydrocarbon contamination issues; analytical methodologies and site assessment for hydrocarbon contaminated soils and groundwater; environmental fate and modeling; remedial technologies for hydrocarbon contaminated soils and groundwater; and risk assessment and risk management

  3. Hydrocarbon Leak Detection Sensor Project

    Data.gov (United States)

    National Aeronautics and Space Administration — FTT is proposing the development of a sensor to detect the presence of hydrocarbons in turbopump Inter-Propellant Seals (IPS). The purpose of the IPS is to prevent...

  4. Predicting hydrocarbon release from soil

    International Nuclear Information System (INIS)

    'Full text:' The remediation of hazardous chemicals from soils can be a lengthy and costly process. As a result, recent regulatory initiatives have focused on risk-based corrective action (RBCA) approaches. Such approaches attempt to identify the amount of chemical that can be left at a site with contaminated soil and still be protective of human health and the environment. For hydrocarbons in soils to pose risk to human heath and the environment, the hydrocarbons must be released from the soil and accessible to microorganisms, earthworms, or other higher level organisms. The sorption of hydrocarbons to soil can reduce the availability of the hydrocarbon to receptors. Typically in soils and sediments, there is an initial fast release of a hydrocarbon from the soil to the aqueous phase followed by a slower release of the remaining hydrocarbon to the aqueous phase. The rate and extent of slow release can influence aqueous hydrocarbon concentrations and the fate and transport of hydrocarbons in the subsurface. Once the fast fraction of the chemical has been removed from the soil, the remaining fraction of a chemical may desorb at a rate that natural mechanisms can attenuate the released hydrocarbon. Hence, active remediation may be needed only until the fast fraction has been removed. However, the fast fraction is a soil and chemical specific parameter. This presentation will present a tier I type protocol that has been developed to quickly estimate the fraction of hydrocarbons that are readily released from the soil matrix to the aqueous phase. Previous research in our laboratory and elsewhere has used long-term desorption (four months) studies to determine the readily released fraction. This research shows that a single short-term (less than two weeks) batch extraction procedure provides a good estimate of the fast released fraction derived from long-term experiments. This procedure can be used as a tool to rapidly evaluate the release and bioavailability of

  5. Maritime hydrocarbon pollution: Intervention

    International Nuclear Information System (INIS)

    The possibility of oil spills is of great concern to Canada because of the large quantities of petroleum that are shipped along its long coastline, the economic importance of fishing and other industries that could be affected by an oil spill, and the severity of climatic conditions in Canadian waters. Measures implemented to handle oil spill emergencies include relevant provisions in the merchant marine laws, establishment of a compensation fund for oil spill cleanup and damage, and provision of oil spill-related services by the Canadian Coast Guard (CCG), whose activities in this regard are summarized. The CCG has a fleet of 119 ships, 4 hydrofoils, 35 helicopters, and various small craft as well as oil spill pollution cleanup equipment worth $35 million stationed at 55 locations across Canada and staff specialists in oil spill emergencies. The CCG is responsible for enforcing the merchant marine law and has created a service for intervening in maritime emergencies. The CCG's equipment includes units for pumping out tankers in an emergency situation, shoreline cleanup devices, skimmers, containment booms, and facilities for adding dispersants to spills. A description of the behavior of hydrocarbons in an oil spill at sea is also included. 26 figs

  6. HYDROCARBONS RESERVES IN VENEZUELA

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Cruz, D.J.

    2007-07-01

    Venezuela is an important player in the energy world, because of its hydrocarbons reserves. The process for calculating oil and associated gas reserves is described bearing in mind that 90% of the gas reserves of Venezuela are associated to oil. Likewise, an analysis is made of the oil reserves figures from 1975 to 2003. Reference is also made to inconsistencies found by international experts and the explanations offered in this respect by the Ministry of Energy and Petroleum (MENPET) and Petroleos de Venezuela (PDVSA) regarding the changes that took place in the 1980s. In turn, Hubbert's Law is explained to determine peak production of conventional oil that a reservoir or field will reach, as well as its relationship with remaining reserves. Emphasis is placed on the interest of the United Nations on this topic. The reserves of associated gas are presented along with their relationship with the different crude oils that are produced and with injected gas, as well as with respect to the possible changes that would take place in the latter if oil reserves are revised. Some recommendations are submitted so that the MENPET starts preparing the pertinent policies ruling reserves. (auth)

  7. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.

    1980-08-01

    A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

  8. Aliphatic hydrocarbons of the fungi.

    Science.gov (United States)

    Weete, J. D.

    1972-01-01

    Review of studies of aliphatic hydrocarbons which have been recently detected in the spores of phytopathogenic fungi, and are found to be structurally very similar to the alkanes of higher plants. It appears that the hydrocarbon components of the few mycelial and yeast forms reported resemble the distribution found in bacteria. The occurence and distribution of these compounds in the fungi is discussed. Suggested functional roles of fungal spore alkanes are presented.

  9. The mechanisms of platinum-catalyzed silicon nanowire growth

    International Nuclear Information System (INIS)

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire. (paper)

  10. The mechanisms of platinum-catalyzed silicon nanowire growth

    Science.gov (United States)

    Hibst, N.; Knittel, P.; Biskupek, J.; Kranz, C.; Mizaikoff, B.; Strehle, S.

    2016-02-01

    Platinum (Pt) has been known as a catalyst material for vapor-liquid-solid (VLS) synthesis since the mid 1960s with the potential to grow electronic grade silicon nanowires (SiNWs). In contrast to gold-based growth, Pt-catalyzed SiNW synthesis has rarely been studied, most likely due to higher synthesis temperatures and the formation of multiple Pt silicide phases. Here we present the growth of SiNWs from a Pt catalyst deposited by a focused ion or electron beam, which opens new strategies for the assembly of Pt-catalyzed SiNW-based devices, as well as SiNW growth from Pt nanoparticles and thin films. We show that single-crystalline SiNWs exhibit either the well-known catalyst tip or a polycrystalline silicon tip so far not reported. The local Pt concentration was found to be one key parameter triggering the growth mode. The proposed growth model for both types of SiNWs is based on a solid-state silicide-mediated crystallization rather than VLS. The discussion of the growth modes is supported by a variation of several growth parameters and SiNW synthesis using the substrate materials silicon nitride, single-crystalline silicon, fused silica, and sapphire.

  11. Technology for Efficient Usage of Hydrocarbon-Containing Waste in Production of Multi-Component Solid Fuel

    OpenAIRE

    B. M. Khroustalev; A. N. Pekhota

    2016-01-01

    The paper considers modern approaches to usage of hydrocarbon-containing waste as energy resources and presents description of investigations, statistic materials, analysis results on formation of hydrocarbon-containing waste in the Republic of Belarus. Main problems pertaining to usage of waste as a fuel and technologies for their application have been given in the paper. The paper describes main results of the investigations and a method for efficient application of viscous hydrocarbon-cont...

  12. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  13. Pinacol Coupling Reactions Catalyzed by Active Zinc

    Institute of Scientific and Technical Information of China (English)

    Hui ZHAO; Wei DENG; Qing Xiang GUO

    2005-01-01

    Pinacol coupling reactions catalyzed by active zinc revealed high activity and extensive suitability. The efficiency of the reaction was improved apparently owing to decreasing reductive potential of zinc. In addition, the results indicated that the zinc activity has a direct relation to the coupling reactivity compared to untreated zinc or other general active zinc.

  14. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  15. Sulfilimimines in metal-catalyzed redox reactions

    Czech Academy of Sciences Publication Activity Database

    Voltrová, Svatava; Šrogl, Jiří

    Praha : -, 2009. s. 593-593. ISBN 978-80-02-02160-5. [ESOC 2009. European Symposium on Organic Chemistry /16./. 12.07.2009-16.07.2009, Praha] Institutional research plan: CEZ:AV0Z40550506 Keywords : sulfilimines * metal catalyzed oxidations * benzoisothiazolone Subject RIV: CC - Organic Chemistry

  16. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  17. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    Science.gov (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  18. Alteration and Reformation of Hydrocarbon Reservoirs and Prediction of Remaining Potential Resources in Superimposed Basins

    Institute of Scientific and Technical Information of China (English)

    PANG Hong; PANG Xiongqi; YANG Haijun; LIN Changsong; MENG Qingyang; WANG Huaijie

    2010-01-01

    Complex hydrocarbon reservoirs developed widely in the superimposed basins of China formed from multiple structural alterations,reformation and destruction of hydrocarbon reservoirs formed at early stages.They are characterized currently by trap adjustment,component variation,phase conversion,and scale reformation.This is significant for guiding current hydrocarbon exploration by revealing evolution mechanisms after hydrocarbon reservoir formation and for predicting remaining potential resources.Based on the analysis of a number of complex hydrocarbon reservoirs,there are four geologic features controlling the degree of destruction of hydrocarbon reservoirs formed at early stages:tectonic event intensity,frequency,time and caprock sealing for oil and gas during tectonic evolution.Research shows that the larger the tectonic event intensity,the more frequent the tectonic event,the later the last tectonic event,the weaker the caprock sealing for oil and gas,and the greater the volume of destroyed hydrocarbons in the early stages.Based on research on the main controlling factors of hydrocarbon reservoir destruction mechanisms,a geological model of tectonic superimposition and a mathematical model evaluating potential remaining complex hydrocarbon reservoirs have been established.The predication method and technical procedures were applied in the Tazhong area of Tarim Basin,where four stages of hydrocarbon accumulation and three stages of hydrocarbon alteration occurred.Geohistorical hydrocarbon accumulation reached 3.184billion tons,of which 1.271 billion tons were destroyed.The total volume of remaining resources available for exploration is~1.9 billion tons.

  19. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    International Nuclear Information System (INIS)

    An aggregation growth model of three species A, B and C with the competition between catalyzed birth and catalyzed death is proposed. Irreversible aggregation occurs between any two aggregates of the like species with the constant rate kernels In(n = 1,2,3). Meanwhile, a monomer birth of an A species aggregate of size k occurs under the catalysis of a B species aggregate of size j with the catalyzed birth rate kernel K(k,j) = Kkjv and a monomer death of an A species aggregate of size k occurs under the catalysis of a C species aggregate of size j with the catalyzed death rate kernel L(k,j)=Lkjv, where v is a parameter reflecting the dependence of the catalysis reaction rates of birth and death on the size of catalyst aggregate. The kinetic evolution behaviours of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A species ak(t) is found to be dependent crucially on the competition between the catalyzed birth and death of A species, as well as the irreversible aggregation processes of the three species: (1) In the v k(t) satisfies the conventional scaling form; (2) In the v ≥ 0 case, the competition between the catalyzed birth and death dominates the process. When the catalyzed birth controls the process, ak(t) takes the conventional or generalized scaling form. While the catalyzed death controls the process, the scaling description of the aggregate size distribution breaks down completely

  20. Studies of the Methanol to-hydrocarbon (MTH) reaction over new 8- and 10-ring acidic zeolites

    OpenAIRE

    2009-01-01

    Abstract Developing a process in which natural gas, coal and biomass can be converted to valuable petrochemical products is becoming increasingly important. The methanolto-hydrocarbon (MTH) reactions constitute the final step in one such route. The MTH reaction is catalyzed by acidic zeolites. ZSM-22 zeolite is a less studied catalyst for the MTH reaction and has unidirectional non-interacting channels of 4.6 x 5.7 Å dimensions. In this work, ZSM-22 zeolite previously believed to b...

  1. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak

    2015-08-01

    Full Text Available Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes.

  2. Hydrocarbon potential of Middle Eocene carbonates, Sirt Basin, Libya

    Science.gov (United States)

    Swei, Giuma H.; Tucker, Maurice E.

    2015-11-01

    Deposition of Middle Eocene carbonates in the Sirt Basin in Libya has been the subject of considerable study in recent years because of the importance of sediments of this age as hydrocarbon reservoirs. The Gialo Formation is an important gas-producing reservoir in the Assumood, Sahl and other nearby fields. The gas which is generated from the gas-prone Sirt Shale source rock of the northern Ajdabiya Trough probably migrated in to the Assumood Ridge from the northeast through late Cretaceous, Paleocene and early Eocene carbonates, before being trapped beneath the Augila Shale (Upper Eocene) which is the principal regional seal in the area. This integrated study has enhanced our understanding of reservoir heterogeneity and hydrocarbon potential of the Gialo carbonates and should lead to improved exploration in the future. Reservoir quality in the Gialo Formation is a function of grain types, pore types, grain size, sorting, cementation and compaction, and predicting areas of high reservoir quality has proved difficult; exploration should be oriented to positioning wells into the main trend of the mid-ramp, nummulite accumulation. Different nummulite facies can be reservoirs depending on their diagenetic history. A diagenetic reduction in porosity must be distinguished from a lack of porosity resulting from an unfavourable depositional environment, so that exploration alternatives can be assessed. This integrated study has demonstrated the presence of suitable reservoir rocks, hydrocarbon traps and the close proximity of potential source rocks. These features should encourage further hydrocarbon exploration in the area.

  3. Biodegradation of an oil-hydrocarbon contaminated soil, enhanced by surfactants: Effect of the type and dose of surfactant

    International Nuclear Information System (INIS)

    The aim of this work was to study the effect of different parameters, such as surfactant type an dose, soil initial hydrocarbons concentration, and soil granulometry, over the total petroleum hydrocarbons TPH degradation, as well as over the microbial count (as colony formation units CFU/g soil) along the process. (Author)

  4. Biodegradation of an oil-hydrocarbon contaminated soil, enhanced by surfactants: Effect of the type and dose of surfactant

    Energy Technology Data Exchange (ETDEWEB)

    Torres, L. G.; Galindo, C.; Rojas, N.; Iturbe, R.

    2009-07-01

    The aim of this work was to study the effect of different parameters, such as surfactant type an dose, soil initial hydrocarbons concentration, and soil granulometry, over the total petroleum hydrocarbons TPH degradation, as well as over the microbial count (as colony formation units CFU/g soil) along the process. (Author)

  5. EUV photochemical production of unsaturated hydrocarbons: implications to EUV photochemistry in Titan and Jovian planets.

    Science.gov (United States)

    Imanaka, Hiroshi; Smith, Mark A

    2009-10-22

    The EUV photochemistry of methane is one of the dominant chemical processes in the upper atmospheres of Titan and Jovian planets. The dilution of CH(4) with N(2) significantly changes the subsequent hydrocarbon chemistry initiated by EUV photoionization. At wavelengths below 80 nm, the presence of the dominant N(2) species in a N(2)/CH(4) gas mixture (=95/5) selectively enhances the formation of unsaturated hydrocarbons, such as benzene and toluene, while pure CH(4) gas leads to a wide mixture of saturated/unsaturated hydrocarbon species. This enhanced formation of unsaturated hydrocarbons is most likely initiated by the generation of CH(3)(+) via a dissociative charge-transfer reaction between N(2)(+) and CH(4). This mechanism was further confirmed with the dilution of CH(4) with Ar, which shows similarly enhanced formation of unsaturated species from an Ar/CH(4) (=95/5) gas mixture. In contrast, the depleted generation of unsaturated species from a H(2)/CH(4) gas mixture (=95/5) suggests that the CH(5)(+) ion generated via a proton-transfer reaction is not an important precursor in the production of complex unsaturated hydrocarbons. Therefore, it is the dissociative charge-transfer reaction of CH(4) that initiates the formation of unsaturated complex hydrocarbons through production of C(2)H(5)(+) with subsequent dissociative recombination. Implications regarding photochemistry in the upper atmospheres of Titan and the Jovian planets are discussed. PMID:19673465

  6. Hydrocarbons as markers for identifying postirradiated peanuts

    International Nuclear Information System (INIS)

    Hydrocarbons produced by γ-radiation of peanuts were analyzed to determine the relationship between irradiation and production of hydrocarbons, and the use of hydrocarbons as markers for identifying postirradiated peanuts. Hydrocarbons in peanuts were determined by a sequential procedure of lipid extraction by hexane, Florisil column chromatography, and gas chromatography. Hydrocarbons C17:1, C16:2, C17:2, and C16:3 were easily detected in peanuts irradiated at 0.5 kGy or higher, but not in unirradiated ones. The hydrocarbons were minimally changed by roasting the irradiated peanuts and were not detected in unirradiated roasted peanuts

  7. Frequency of genes in aromatic and aliphatic hydrocarbon biodegradation pathways within baterial populations from Alaskan sediments

    International Nuclear Information System (INIS)

    Bacteria from sediments affected by the Exxon Valdez oil spill were examined for their ability to metabolize aliphatic and aromatic hydrocarbons and for genes in the pathways for metabolism of low molecular weight alkanes and aromatic hydrocarbons. The abilities of microorganisms from Alaskan sediments to mineralize hexadecane and naphthalene were also determined. Microorganisms were further examined for the presence of the alkB gene that codes for the alkane hydroxylase responsible for the hydroxylation of C6-12 alkanes within the pathway for alkane metabolism, and for the presence of the xylE gene that codes for catechol 2,3-dioxygenase that catalyzes the cleavage of catechols within the lower pathway of aromatic hydrocarbon metabolism. These studies were aimed at determining whether microorganisms can possess genes in the pathways for both aromatic and aliphatic hydrocarbon metabolism. It was found that a significant proportion of the naturally occurring hydrocarbon-degrading populations within Alaskan sediments affected by the Exxon Valdez oil spill had both the xylE and alkB genes and could convert hexadecane and naphthalene to CO2. A greater proportion had xylE than alkB, reflecting the composition of the residual oil at the time of sampling. Nearly equal populations with xylE alone, alkB alone, and xylE plus alkB genes together were found after exposure to fresh crude oil. Populations with xylE lacking alkB increased after enrichment on naphthalene. Thus, the genotypes of hydrocarbon-degrading populations reflected the composition of the hydrocarbons to which they were exposed. 13 refs., 3 figs., 1 tab

  8. Enrichment of light hydrocarbon mixture

    Science.gov (United States)

    Yang, Dali; Devlin, David; Barbero, Robert S.; Carrera, Martin E.; Colling, Craig W.

    2011-11-29

    Light hydrocarbon enrichment is accomplished using a vertically oriented distillation column having a plurality of vertically oriented, nonselective micro/mesoporous hollow fibers. Vapor having, for example, both propylene and propane is sent upward through the distillation column in between the hollow fibers. Vapor exits neat the top of the column and is condensed to form a liquid phase that is directed back downward through the lumen of the hollow fibers. As vapor continues to ascend and liquid continues to countercurrently descend, the liquid at the bottom of the column becomes enriched in a higher boiling point, light hydrocarbon (propane, for example) and the vapor at the top becomes enriched in a lower boiling point light hydrocarbon (propylene, for example). The hollow fiber becomes wetted with liquid during the process.

  9. Parameters critical to muon-catalyzed fusion

    International Nuclear Information System (INIS)

    We have demonstrated that muon catalysis cycling rates increase rapidly with increasing deuterium-tritium gas temperatures and densities. Furthermore, muon-capture losses are significantly smaller than predicted before the experiments. There remains a significant gap between observation and theoretical expectation for the muon-alpha sticking probability in dense d-t mixtures. We have been able to achieve muon-catalyzed yields of 150 fusion/muon (average). While the fusion energy thereby released significantly exceeds expectations, enhancements by nearly a factor of twenty would be needed to realize energy applications for a pure (non-hybrid) muon-catalyzed fusion reactor. The process could be useful in tritium-breeding schemes. We have also explored a new form of cold nuclear fusion which occurs when hydrogen isotopes are loaded into metals. 22 refs., 10 figs

  10. A novel DNA joining activity catalyzed by T4 DNA ligase.

    OpenAIRE

    Western, L M; Rose, S. J.

    1991-01-01

    The use of T4 and E. coli DNA ligases in genetic engineering technology is usually associated with nick-closing activity in double stranded DNA or ligation of 'sticky-ends' to produce recombinant DNA molecules. We describe in this communication the ability of T4 DNA ligase to catalyze intramolecular loop formation between annealed oligodeoxyribonucleotides wherein Watson-Crick base pairing is absent on one side of the ligation site. Enzyme concentration, loop size, substrate specificity, and ...

  11. Direct amidation of amino acid derivatives catalyzed by arylboronic acids : applications in dipeptide synthesis.

    OpenAIRE

    Liu, S.; Yang, Y.; Liu, X.; Ferdousi, F. K.; Batsanov, A.S.; Whiting, A

    2013-01-01

    The direct amidation of amino acid derivatives catalyzed by arylboronic acids has been examined. The reaction was generally slow relative to simple amine-carboxylic acid combinations though proceeded at 65–68 °C generally avoiding racemization. 3,4,5-Trifluorophenylboronic and o-nitrophenylboronic acids were found to be the best catalysts, though for slower dipeptide formations, high catalyst loadings were required and an interesting synergistic catalytic effect between two arylboronic acids ...

  12. Recent advances in copper-catalyzed C-H bond amidation.

    Science.gov (United States)

    Wan, Jie-Ping; Jing, Yanfeng

    2015-01-01

    Copper catalysis has been known as a powerful tool for its ubiquitous application in organic synthesis. One of the fundamental utilities of copper catalysis is in the C-N bond formation by using carbon sources and nitrogen functional groups such as amides. In this review, the recent progress in the amidation reactions employing copper-catalyzed C-H amidation is summarized. PMID:26664644

  13. C-H bond halogenation catalyzed or mediated by copper: an overview.

    Science.gov (United States)

    Hao, Wenyan; Liu, Yunyun

    2015-01-01

    Carbon-halogen (C-X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C-X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C-X (X = F, Cl, Br, I) bond formation via direct C-H bond transformation is reviewed. PMID:26664634

  14. Why You Really Should Consider Using Palladium-Catalyzed Cross-Coupling of Silanols and Silanolates

    OpenAIRE

    Denmark, Scott E.; Ambrosi, Andrea

    2015-01-01

    The transition metal-catalyzed cross-coupling of organometallic nucleophiles derived from tin, boron, and zinc with organic electrophiles enjoys a preeminent status among modern synthetic methods for the formation of carbon-carbon bonds. In recent years, organosilanes have emerged as viable alternatives to the conventional reagents, with the added benefits of low cost, low toxicity and high chemical stability. However, silicon-based cross-coupling reactions often require heating in the presen...

  15. Ru Catalyzed Alkene-Alkyne Coupling. Total Synthesis of Amphidinolide P

    OpenAIRE

    Trost, Barry M.; Papillon, Julien P. N.; Nussbaumer, Thomas

    2005-01-01

    A coordinatively unsaturated ruthenium complex catalyzed the formation of a carbon-carbon bond between two judiciously chosen alkene and alkyne partners in good yield, and in a chemo- and regioselective fashion, in spite of the significant degree of unsaturation of the substrates. The resulting 1,4-diene forms the backbone of the cytotoxic marine natural product amphidinolide P. The alkene partner was rapidly assembled from (R)-glycidyl tosylate, which served as a linchpin in a one-flask, seq...

  16. Copper Catalyzed Oceanic Methyl Halide Production

    OpenAIRE

    Robin Kim, Jae Yun; Rhew, Robert

    2014-01-01

    Methyl halides are found in all of Earth’s biomes, produced naturally or through manmade means. Their presence in the atmosphere is problematic, as they catalyze depletion of stratospheric ozone. To understand the full environmental impact of these compounds, it is important to identify their chemical cycling processes. Iron increases methyl halide production in soils and oceans, yet copper’s influence remains unknown despite its similar chemical oxidation properties to iron. I experimentally...

  17. Antibody-Catalyzed Degradation of Cocaine

    Science.gov (United States)

    Landry, Donald W.; Zhao, Kang; Yang, Ginger X.-Q.; Glickman, Michael; Georgiadis, Taxiarchis M.

    1993-03-01

    Immunization with a phosphonate monoester transition-state analog of cocaine provided monoclonal antibodies capable of catalyzing the hydrolysis of the cocaine benzoyl ester group. An assay for the degradation of radiolabeled cocaine identified active enzymes. Benzoyl esterolysis yields ecgonine methyl ester and benzoic acid, fragments devoid of cocaine's stimulant activity. Passive immunization with such an artificial enzyme could provide a treatment for dependence by blunting reinforcement.

  18. Palladium(II)-Catalyzed Coupling Reactions

    OpenAIRE

    Lindh, Jonas

    2010-01-01

    Sustainable chemical processes are becoming increasingly important in all fields of synthetic chemistry. Catalysis can play an important role in developing environmentally benign chemical processes, and transition metals have an important role to play in the area of green chemistry. In particular, palladium(II) catalysis includes many key features for successful green chemistry methods, as demonstrated by a number of eco-friendly oxidation reactions catalyzed by palladium(II). The aim of the ...

  19. Palladium-catalyzed oxidative carbonylation reactions.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2013-02-01

    Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

  20. Determination of the hydrocarbon-degrading metabolic capabilities of tropical bacterial isolates

    Energy Technology Data Exchange (ETDEWEB)

    Marquez-Rocha, F.J.; Olmos-Soto, J. [Centro de Investigacion Cientifica y de Educacion Superior de Ensenada, San Diego, CA (United States). Departamento de Biotecnologia Marina; Rosano-Hernandez, M.A.; Muriel-Garcia, M. [Instituto Mexicano del Petroleo, CD Carmen Camp (Mexico). Zona Marina/Tecnologia Ambiental

    2005-01-01

    Of more than 20 bacteria isolated from a tropical soil using minimal medium supplemented with hydrocarbons, 11 grew well on diesel as sole carbon source, and another 11 grew in the presence of polynuclear aromatic hydrocarbons (PAHs). Ten isolates were identified phenotypically as Pseudomonas sp. and eight as Bacillus sp. Gene sequences representing the catabolic genes (alkM, todM, ndoM, and xylM) and 16S rRNA gene sequences characteristic for Pseudomona and Bacillus were amplified by PCR, using DNA recovered from the supernatant of hydrocarbon-contaminated soil suspensions. Based on their rapid growth characteristics in the presence of hydrocarbons and the formation of PCR products for the catabolic genes alkM and ndoM six isolates were selected for biodegradation assays. After 30 days a mixed culture of two isolates achieved close to 70% hydrocarbon removal and apparent mineralization of 16% of the hydrocarbons present in the soil. Biodegradation rates varied from 275 to 387 mg hydrocarbon kg{sup -1} day{sup -1}. Several bacterial isolates obtained in this study have catabolic capabilities for the biodegradation of alkanes and aromatic hydrocarbons including PAHs. (author)

  1. Electron microscopy of hydrocarbon production in parthenium argentatum (guayule)

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, T.E.

    1977-11-01

    The electron microscope was used to study the biological processes involved in hydrocarbon production. The little desert shrub Guayule (Parthenium argentatum) was selected for study. This shrub can produce hydrocarbons (rubber) in concentrations up to 1/4 of its dry weight. It grows on semi-arid land and has been extensively studied. The potential of Guayule is described in detail. Results of an investigation into the morphology of Guayule at the electron microscope level are given. Experiments, which would allow the biosynthesis of hydrocarbon in Guayule to be followed, were designed. In order to do this, knowledge of the biochemistry of rubber formation was used to select a tracer, mevalonic acid. Mevalonic acid is the precursor of all the terpenoids, a large class of hydrocarbons which includes rubber. It was found that when high enough concentrations of mevalonic acid are administered to seedling Guayule plants, build-ups of metabolized products are found within the chloroplasts of the seedlings. Also, tritium labeled mevalonic acid was used as a precursor, and its metabolic progress was followed by using the technique of electron microscope autoradiography. The results of these experiments also implicated chloroplasts of the Guayule plant in hydrocarbon production. The final task was the development of a system to produce three-dimensional stereo reconstructions of organelles suspected of involvement in hydrocarbon biosynthesis in Guayule. The techniques are designed to reconstruct an object from serial sections of that object. The techniques use stereo imaging both to abstract information for computer processing, and also in the computer produced reconstruction.

  2. Magnetic Susceptibility Measurements as a Proxy for Hydrocarbon Biodegradation

    Science.gov (United States)

    Mewafy, F.; Atekwana, E. A.; Slater, L. D.; Werkema, D.; Revil, A.; Ntarlagiannis, D.; Skold, M.

    2011-12-01

    Magnetic susceptibility (MS) measurements have been commonly used in paleoclimate studies, as a proxy for environmental pollution such as heavy metal contamination, and for delineating zones of oil seeps related to hydrocarbon exploration. Few studies have assessed the use of MS measurements for mapping zones of oil pollution. In this study, we investigated the variation in magnetic susceptibility across a hydrocarbon contaminated site undergoing biodegradation. Our objective was to investigate if MS measurements could be used as a proxy indicator of intrinsic bioremediation linked to the activity of iron reducing bacteria. An improved understanding of the mechanisms generating geophysical signatures associated with microbial enzymatic activity could permit the development of geophysical imaging technologies for long-term, minimally invasive and sustainable monitoring of natural biodegradation at oil spill sites. We used a Bartington MS probe to measure MS data along fifteen boreholes within contaminated (both free phase and dissolved phase hydrocarbon plumes) and clean areas. Our results show the following: (1) an enhanced zone of MS straddling the water table at the contaminated locations, not observed at the clean locations; (2) MS values within the free product plume are higher compared to values within the dissolved product plume; (3) the MS values within the vadoze zone above the free product plume are higher compared to values within the dissolved product plume; 4) the zone of high MS is thicker within the free product plume compared to the dissolved product plume. We suggest that the zone of enhanced MS results from the precipitation of magnetite related to the oxidation of the hydrocarbons coupled to iron reduction. Our data documents a strong correlation between MS and hydrocarbon concentration. We conclude that recognition of these zones of enhanced magnetite formation allows for the application of MS measurements as a: (1) low cost, rapid monitoring

  3. Formation and distribution of polycyclic aromatic hydrocarbons during large size coal pyrolysis%大尺度煤热解多环芳烃生成及排放规律

    Institute of Scientific and Technical Information of China (English)

    刘淑琴; 靳志伟; 张尚军; 王媛媛; 李亚辉; 曾艳菊; 张宇; 易荣; 李秀秀

    2012-01-01

    Being an important process of coal fires and underground coal gasification, coal seam pyrolysis is a crucial source of PAHs discharging into the air. Four kinds of low rank coals were pyrolyzed in the horizontal tube furnace to simulate coal seam pyrolysis ,and the formation and distribution of the 16 kinds of US EPA prior controlled PAHs at different temperatures were studied. The results show that with temperature increasing, four kinds of large size coals produce PAHs continually and PAHs yield is remarkably affected by temperature. 3-ring PAHs are the main species which takes up more than 80%. The yield of 2-ring PAHs attains the maximum at 400 ~C , and decreases rapidly with increasing temperature. Above 700 ~C, the yield of 4-ring PAHs rises significantly, and the yields of 5-ring and 6-ring are less than 1.0 mg/kg. The formation of the most toxic specie, benzo(a) pyrene, peaks between 500-700℃, and the maximum discharge of Dibenz( a, h)anthracene occurs at 400℃. Resistance of heat conduction and mass transfer dur- ing the low speed pyrolysis process for the large size coal is the main affecting factor for the formation and discharge of PAHs. With the coal rank increasing, the discharge of toxic PAHs is enhanced. The maximum of TEQ occurs at 400 and 900 ℃.%煤层热解是煤田火灾和煤层气化的重要过程,也是多环芳烃(PAHs)生成及排放的重要来源。选用4种低变质煤,在水平管式炉内进行煤层热解模拟实验,研究了16种USEPA优控PAHs在不同热解温度条件下的生成和分布特征。结果表明:PAHs的生成受热解温度的影响显著。热解产物中PAHs分布以3环PAHs为主,占80%以上;2环萘的生成随热解温度的升高快速下降;热解温度高于700℃时,4环类PAHs生成显著增加;5环、6环类PAHs生成量小于1.0mg/kg;高毒性苯并(a)芘的峰值出现在500~700℃,二苯并(a,h)蒽在400℃时生成量最大。热传导及传

  4. The performance of ammonium exchanged zeolite for the biodegradation of petroleum hydrocarbons migrating in soil water.

    Science.gov (United States)

    Freidman, Benjamin L; Gras, Sally L; Snape, Ian; Stevens, Geoff W; Mumford, Kathryn A

    2016-08-01

    Nitrogen deficiency has been identified as the main inhibiting factor for biodegradation of petroleum hydrocarbons in low nutrient environments. This study examines the performance of ammonium exchanged zeolite to enhance biodegradation of petroleum hydrocarbons migrating in soil water within laboratory scale flow cells. Biofilm formation and biodegradation were accelerated by the exchange of cations in soil water with ammonium in the pores of the exchanged zeolite when compared with natural zeolite flow cells. These results have implications for sequenced permeable reactive barrier design and the longevity of media performance within such barriers at petroleum hydrocarbon contaminated sites deficient in essential soil nutrients. PMID:27132074

  5. Total Petroleum Hydrocarbons (TPH): ToxFAQs

    Science.gov (United States)

    ... a state: This map displays locations where Total Petroleum Hydrocarbons (TPH) is known to be present. On ... I get more information? ToxFAQs TM for Total Petroleum Hydrocarbons (TPH) ( Hidrocarburos Totales de Petróleo (TPH) ) August ...

  6. Stability of hydrocarbons at deep Earth pressures and temperatures

    OpenAIRE

    Spanu, Leonardo; Donadio, Davide; Hohl, Detlef; Schwegler, Eric; Galli, Giulia

    2011-01-01

    Determining the thermochemical properties of hydrocarbons (HCs) at high pressure and temperature is a key step toward understanding carbon reservoirs and fluxes in the deep Earth. The stability of carbon-hydrogen systems at depths greater than a few thousand meters is poorly understood and the extent of abiogenic HCs in the Earth mantle remains controversial. We report ab initio molecular dynamics simulations and free energy calculations aimed at investigating the formation of higher HCs from...

  7. Suppression of superoxide anion generation catalyzed by xanthine oxidase with alkyl caffeates and the scavenging activity.

    Science.gov (United States)

    Masuoka, Noriyoshi; Kubo, Isao

    2016-05-01

    Alkyl caffeates are strong antioxidants and inhibitors of xanthine oxidase. However, it is unclear about the effect of caffeic acid and alkyl caffeates on superoxide anion (O2(-)) generation catalyzed by xanthine oxidase. Effects of caffeic acid and alkyl caffeates on the uric acid formation and O2(-) generation catalyzed by xanthine oxidase were analyzed. The scavenging activities of 1,1-diphenyl-2-picryhydrazyl (DPPH) radical and O2(-) generated with phenazine methosulfate (PMS) and NADH were examined. Caffeic acid derivatives equally suppressed O2(-) generation, and the suppression is stronger than inhibition of xanthine oxidase. Scavenging activity of O2(-) is low compared to the suppression of O2(-) generation. Suppression of O2(-) generation catalyzed by xanthine oxidase with caffeic acid derivatives was not due to enzyme inhibition or O2(-) scavenging but due to the reduction of xanthine oxidase molecules. Alkyl caffeates are effective inhibitors of uric acid and O2(-) catalyzed by xanthine oxidase as well as antioxidants for edible oil. PMID:26940252

  8. Rh(iii)-catalyzed chemoselective C-H functionalizations of tertiary aniline N-oxides with alkynes.

    Science.gov (United States)

    Huang, Xiaolei; Liang, Wenbo; Shi, Yang; You, Jingsong

    2016-05-01

    In this work, we report novel Rh(iii)-catalyzed chemoselective functionalizations of tertiary aniline N-oxides with alkynes, including annulation via the sequential C(sp(2))-H and C(sp(3))-N activation for the formation of N-alkylindoles and an O-atom transfer (OAT) process for the synthesis of acetophenones. PMID:27121366

  9. Comparative investigations of zeolite catalyst deactivation by coking in the conversion of methanol to hydrocarbons

    OpenAIRE

    Evensen, Kjetil Gurholt

    2014-01-01

    With large countries as India and China in tremendous development accompanied by a growing worldwide population, questions arise in how energy demands can be met in the post-oil society. The methanol-to-hydrocarbon process, catalysed by Brønsted acidic zeolites, constitutes an alternative route for the production of gasoline and other valuable hydrocarbons from feedstocks such as natural gas and coal. Catalyst deactivation by coke formation is nevertheless a big concern, and a better understa...

  10. Catalytic hydrogen-chlorine exchange between chlorinated hydrocarbons under oxygen-free conditions

    OpenAIRE

    van der Heijden, A.W.A.M.; Podkolzin, S.G.; Jones, M. E.; Bitter, J.H.; Weckhuysen, B. M.

    2008-01-01

    Chlorinated hydrocarbons (CHCs) remain important industrial chemical intermediates and solvents, especially for the exploration of the potential of La-based materials for the conversion of chlorinated waste compounds.[1] The production of industrially important CHCs frequently occurs with concurrent formation of less desirable side-products. For example, mixtures of chlorinated C1 and C2 hydrocarbons are still formed as by-products in industrial processes such as the production of vinyl chlor...

  11. Control of facies/potential on hydrocarbon accumulation:a geological model for Iacustrine rift basins

    Institute of Scientific and Technical Information of China (English)

    Chen Dongxia; Pang Xiongqi; Zhang Shanwen; Wang Yongshi; Zhang Jun

    2008-01-01

    The formation and distribution of hydrocarbon accumulations are jointly controlled by"stratigraphic facies"and"fluid potential",which can be abbreviated in"control of facies/potential on hydrocarbon accumulation".Facies and potential control the time-space distribution of hydrocarbon accumulation macroscopically and the petroliferous characteristics of hydrocarbon accumulation microscopically.Tectonic facies and sedimentary facies control the time-space distribution.Lithofacies and petrophysical facies control the petroliferous characteristics.Favorable facies and high porosity and permeability control hydrocarbon accumulation in the lacustrine rift basins in China.Fluid potential is represented by the work required,which comprises the work against gravity,pressure,interfacial energy and kinetic energy.Hydrocarbon migration and accumulation are controlled by the joint action of multiple driving forces,and are characterized by accumulation in the area of low potential.At the structural high,low geopotential energy caused by buoyancy control anticlinal reservoir.The formation of lithological oil pool is controlled by low interfacial energy caused by capillary force.Low compressive energy caused by overpressure and faulting activity control the formation of the faulted block reservoir.Low geopotential energy of the basin margin caused by buoyancy control stratigraphic reservoir.The statistics of a large number of oil reservoirs show that favorable facies and low potential control hydrocarbon accumulation in the rift basin.where over 85% of the discovered hydrocarbon accumulations are distributed in the trap with favorable facies and lOW potentials.The case study showed that the prediction of favorable areas by application of the near source-favorable facies-low potential accumulation model correlated well with over 90% of the discovered oil pools' distribution of the middle section of the third member of the Shahejie Formation in the Dongying Depression,Bohai Bay

  12. Observations of the release of non-methane hydrocarbons from fractured shale

    OpenAIRE

    Sommariva, Roberto; Blake, Robert S.; Cuss, Robert J.; Cordell, Rebecca L.; Harrington, Jon F.; White, Iain R.; Monks, Paul S.

    2014-01-01

    The organic content of shale has become of commercial interest as a source of hydrocarbons, owing to the development of hydraulic fracturing (“fracking”). While the main focus is on the extraction of methane, shale also contains significant amounts of non-methane hydrocarbons (NMHCs). We describe the first real-time observations of the release of NMHCs from a fractured shale. Samples from the Bowland-Hodder formation (England) were analyzed under different conditions using mass spectrometry, ...

  13. Synthesis of isoquinolines via Rh-catalyzed C-H activation/C-N cyclization with diazodiesters or diazoketoesters as a C2 source.

    Science.gov (United States)

    Wang, Jie; Zha, Shanke; Chen, Kehao; Zhang, Feifei; Zhu, Jin

    2016-06-01

    Synthesis of isoquinolines based on efficient C-C and C-N bond formation through Rh(iii)-catalyzed C-H activation and subsequent intramolecular cyclization is reported. Diazodiesters serving as a C2 source in the newly formed heterocycles are first demonstrated. Additionally, the Rh(iii)-catalyzed direct C-H activation/cyclization of benzimidates with diazoketoesters is also described. PMID:27146107

  14. Weathered Hydrocarbon Wastes: A Risk Management Primer

    OpenAIRE

    Brassington, Kirsty J.; Hough, Rupert L.; Paton, Graeme I.; Semple, Kirk T.; Risdon, Graeme C.; Crossley, Jane; Hay, I; Askari, K.; Pollard, Simon J. T.

    2007-01-01

    We provide a primer and critical review of the characterization, risk assessment, and bioremediation of weathered hydrocarbons. Historically the remediation of soil contaminated with petroleum hydrocarbons has been expressed in terms of reductions in total petroleum hydrocarbon (TPH) load rather than reductions in risk. There are several techniques by which petroleum hydrocarbons in soils can be characterized. Method development is often driven by the objectives of published...

  15. TRANSGRESSION FAN DELTAS IN THE SECOND MEMBER OF ZHUHAI FORMATION AND HYDROCARBON ACCUMULATION IN THE ABRUPT SLOPE AREA OF WENCHANG B SAG%文昌B凹陷陡坡带珠海组二段海侵扇三角洲储层特征及油气成藏特征

    Institute of Scientific and Technical Information of China (English)

    张迎朝; 陈志宏; 李绪深; 徐新德

    2011-01-01

    Reservoir depositional model under special tectonic setting of Zhuhai Formation and its pool-forming pattern on the abrupt slope area in Wenchang B sag were studied by means of structure-sequence stratigraphy, sedimentary paleo-morphology, sedimentary micro-facies, and intergraded pool-forming analysis methods. The first and second members of Zhuhai Formation formed a good regional reservoir and cap rock assemblage. The tide-dominated transgression retrograding fan deltas of the second member of Zhuhai Formation is controlled by paleo-mound and swale morphology. The good reservoir property in permeability made the second member of Zhuhai Formation one of major strata for hydrocarbon migration and accumulation. Through the analysis,the main pool-forming factors are controlled by source rock, faults and traps, and the pool-forming pattern is characterized by vertical migration,preferential accumulation and valid sealing fault block. Exploration direction was predicted and proved by drilling recently. A new commercial oil field and several oil-bearing fault blocks were discovered in the abrupt slope area of Wenchang B sag.%利用构造、层序地层、沉积古地貌、沉积微相分析、成藏综合分析等方法,对珠江口盆地文昌B凹陷陡坡带特殊构造背景下的珠海组储层沉积相及其油气成藏模式进行研究,认为该区珠海组二段与珠海组一段构成了一套优质区域性储盖组合,珠海组二段沉积期,在陡坡带古丘地貌上发育潮控海侵退积型扇三角洲相,其水下分流河道骨架砂岩较好的孔渗性使珠海组二段成为油气优势运聚成藏层系,是主要勘探目的层之一.结合烃源岩、沟源断裂及圈闭等成藏主控因素分析,提出该区珠海组二段“垂向运移、优势聚集、有效断块”的油气成藏模式,钻探发现文昌B凹陷陡坡带X构造整装规模储量的商业性油田和一批含油构造.

  16. Effective viscosity of confined hydrocarbons

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, V.N.; Persson, B.N.J.

    2012-01-01

    We present molecular dynamics friction calculations for confined hydrocarbon films with molecular lengths from 20 to 1400 carbon atoms. We find that the logarithm of the effective viscosity ηeff for nanometer-thin films depends linearly on the logarithm of the shear rate: log ηeff=C-nlog γ̇, where...

  17. Treating tar sands formations with dolomite

    Science.gov (United States)

    Vinegar, Harold J.; Karanikas, John Michael

    2013-10-15

    A method for treating a karsted formation containing heavy hydrocarbons and dolomite includes providing heat to at least part of one or more karsted layers in the formation from one or more heaters located in the karsted layers. A temperature in at least one of the karsted layers is allowed to reach a decomposition temperature of dolomite in the formation. The dolomite is allowed to decompose and at least some hydrocarbons are produced from at least one of the karsted layers of the formation.

  18. Promising approaches to the purification of soils and groundwater from hydrocarbons (A Review)

    Science.gov (United States)

    Vodyanitskii, Yu. N.; Trofimov, S. Ya.; Shoba, S. A.

    2016-06-01

    Soils and waters are affected by oil spills in the course of oil production and hydrocarbon leakages because of the corrosion of underground reservoirs, as well as the filtration of hydrocarbons from the tailing ponds formed during the extraction of oil from oil sands. The conventional technology for the withdrawal of contaminated water and its purification on the surface is low-efficient and expensive. New approaches are proposed for the in situ purification of soils and groundwater. To accelerate the oxidation, active substances atypical for the supergenesis zone are used: peroxides of metals and hydrogen. The efficiency of hydrogen peroxide significantly increases when the oxidation is catalyzed by Fe2+ or Fe3+ (Fenton reaction). The effects of Fe(III), sulfates, and carbon dioxide as electron acceptors are studied under anaerobic conditions (with oxygen deficit).

  19. Hydrogen isotope exchange between boranes and deuterated aromatic hydrocarbons: evidence for reversible hydroboration of benzene

    International Nuclear Information System (INIS)

    Pentaborane, B5H9, and diborane, B2H6, undergo hydrogen isotope exchange with deuterated aromatic hydrocarbons. Lewis acid catalyzed hydrogen isotope exchange occurs between benzene-d6 and the apical hydrogen atom of B5H9 to form 1-DB5H8 at ambient temperature. In uncatalyzed exchanges, B5H9 reacts with deuterated aromatic hydrocarbons to produce 1,2,3,4,5-D5B5H4 at +450C and B5D9 at +1200C. This thermally induced hydrogen isotope exchange apparently occurs via a reversible hydroboration of the aromatic ring. Diborane undergoes a similar isotope exchange with benzene-d6 under mild thermal conditions. 18 references, 6 figures, 3 tables

  20. Experimental glomerulonephritis induced by hydrocarbon exposure: A systematic review

    Directory of Open Access Journals (Sweden)

    Ravnskov Uffe

    2005-12-01

    models a causal role of glomerular immune complex formation was unlikely, but may rather have been a secondary phenomenon. As most glomerulonephritis subgroups were seen and as some of the hydrocarbons produced more than one subgroup, the microscopic findings in a patient cannot be used as a clue to the causation of his disease. By the same reason, the lack of a specific histological pattern in patients with glomerulonephritis assumed to have been caused by hydrocarbon exposure is not contradictive.

  1. Contribution of First- versus Second-Generation Products to Secondary Organic Aerosols Formed in the Oxidation of Biogenic Hydrocarbons

    OpenAIRE

    Ng, Nga L.; Kroll, Jesse H.; Keywood, Melita D.; Bahreini, Roya; Varutbangkul, Varuntida; Flagan, Richard C.; Seinfeld, John H.; Lee, Anita; Goldstein, Allen H.

    2006-01-01

    Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase conc...

  2. A phycocyanin·phellandrene synthase fusion enhances recombinant protein expression and β-phellandrene (monoterpene) hydrocarbons production in Synechocystis (cyanobacteria).

    Science.gov (United States)

    Formighieri, Cinzia; Melis, Anastasios

    2015-11-01

    Cyanobacteria can be exploited as photosynthetic platforms for heterologous generation of terpene hydrocarbons with industrial applications. Transformation of Synechocystis and heterologous expression of the β-phellandrene synthase (PHLS) gene alone is necessary and sufficient to confer to Synechocystis the ability to divert intermediate terpenoid metabolites and to generate the monoterpene β-phellandrene during photosynthesis. However, terpene synthases, including the PHLS, have a slow Kcat (low Vmax) necessitating high levels of enzyme concentration to enable meaningful rates and yield of product formation. Here, a novel approach was applied to increase the PHLS protein expression alleviating limitations in the rate and yield of β-phellandrene product generation. Different PHLS fusion constructs were generated with the Synechocystis endogenous cpcB sequence, encoding for the abundant in cyanobacteria phycocyanin β-subunit, expressed under the native cpc operon promoter. In one of these constructs, the CpcB·PHLS fusion protein accumulated to levels approaching 20% of the total cellular protein, i.e., substantially higher than expressing the PHLS protein alone under the same endogenous cpc promoter. The CpcB·PHLS fusion protein retained the activity of the PHLS enzyme and catalyzed β-phellandrene synthesis, yielding an average of 3.2 mg product g(-1) dry cell weight (dcw) versus the 0.03 mg g(-1)dcw measured with low-expressing constructs, i.e., a 100-fold yield improvement. In conclusion, the terpene synthase fusion-protein approach is promising, as, in this case, it substantially increased the amount of the PHLS in cyanobacteria, and commensurately improved rates and yield of β-phellandrene hydrocarbons production in these photosynthetic microorganisms. PMID:26410450

  3. Direct hydrocarbon exploration and gas reservoir development technology

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Young Hoon; Oh, Jae Ho; Jeong, Tae Jin [Korea Inst. of Geology Mining and Materials, Taejon (Korea, Republic of)] [and others

    1995-12-01

    In order to enhance the capability of petroleum exploration and development techniques, three year project (1994 - 1997) was initiated on the research of direct hydrocarbon exploration and gas reservoir development. This project consists of four sub-projects. (1) Oil(Gas) - source rock correlation technique: The overview of bio-marker parameters which are applicable to hydrocarbon exploration has been illustrated. Experimental analysis of saturated hydrocarbon and bio-markers of the Pohang E and F core samples has been carried out. (2) Study on surface geochemistry and microbiology for hydrocarbon exploration: the test results of the experimental device for extraction of dissolved gases from water show that the device can be utilized for the gas geochemistry of water. (3) Development of gas and gas condensate reservoirs: There are two types of reservoir characterization. For the reservoir formation characterization, calculation of conditional simulation was compared with that of unconditional simulation. In the reservoir fluid characterization, phase behavior calculations revealed that the component grouping is more important than the increase of number of components. (4) Numerical modeling of seismic wave propagation and full waveform inversion: Three individual sections are presented. The first one is devoted to the inversion theory in general sense. The second and the third sections deal with the frequency domain pseudo waveform inversion of seismic reflection data and refraction data respectively. (author). 180 refs., 91 figs., 60 tabs.

  4. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    high temperatures and long reaction times. To address this issue, we have developed several new families of carbon- and boron-based ligands, which are even better donors. The corresponding metal complexes (particularly gold, rhodium, iridium, and ruthenium) of all these species will be tested in the Markovnikov and anti-Markovnikov hydroamination of alkynes, allenes, and also alkenes with ammonia and hydrazine. We will also develop metal-free catalytic processes for the functionalization of ammonia and hydrazine. By possessing both a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble and can mimic the chemical behavior of transition metals. Our preliminary results demonstrate that specially designed carbenes can split the N–H bond of ammonia by an initial nucleophilic activation that prevents the formation of Lewis acid-base adducts, which is the major hurdle for the transition metal catalyzed functionalization of NH3. The use of purely organic compounds as catalysts will eliminate the major drawbacks of transition-metal-catalysis technology, which are the excessive cost of metal complexes (metal + ligands) and in many cases the toxicity of the metal.

  5. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.

    Science.gov (United States)

    Yedage, Subhash L; Bhanage, Bhalchandra M

    2016-05-20

    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level. PMID:27088815

  6. Syngas Upgrading to Hydrocarbon Fuels Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Talmadge, M.; Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates the upgrading of woody biomass derived synthesis gas (syngas) to hydrocarbon biofuels. While this specific discussion focuses on the conversion of syngas via a methanol intermediate to hydrocarbon blendstocks, there are a number of alternative conversion routes for production of hydrocarbons through a wide array of intermediates from syngas. Future work will also consider the variations to this pathway to determine the most economically viable and lowest risk conversion route. Technical barriers and key research needs have been identified that should be pursued for the syngas-to-hydrocarbon pathway to be competitive with petroleum-derived gasoline-, diesel- and jet-range hydrocarbon blendstocks.

  7. Biodegradation of petroleum hydrocarbons in hypersaline environments

    Directory of Open Access Journals (Sweden)

    Luiz Fernando Martins

    2012-09-01

    Full Text Available Literature on hydrocarbon degradation in extreme hypersaline media presents studies that point to a negative effect of salinity increase on hydrocarbonoclastic activity, while several others report an opposite tendency. Based on information available in the literature, we present a discussion on the reasons that justify these contrary results. Despite the fact that microbial ability to metabolize hydrocarbons is found in extreme hypersaline media, indeed some factors are critical for the occurrence of hydrocarbon degradation in such environments. How these factors affect hydrocarbon degradation and their implications for the assessment of hydrocarbon biodegradation in hypersaline environments are presented in this review.

  8. Fischer-Tropsch catalysts for the production of hydrocarbon fuels with high selectivity.

    Science.gov (United States)

    Zhang, Qinghong; Cheng, Kang; Kang, Jincan; Deng, Weiping; Wang, Ye

    2014-05-01

    Fischer-Tropsch synthesis is a key reaction in the utilization of non-petroleum carbon resources, such as methane (natural gas, shale gas, and biogas), coal, and biomass, for the sustainable production of clean liquid fuels from synthesis gas. Selectivity control is one of the biggest challenges in Fischer-Tropsch synthesis. This Minireview focuses on the development of new catalysts with controllable product selectivities. Recent attempts to increase the selectivity to C5+ hydrocarbons by preparing catalysts with well-defined active phases or with new supports or by optimizing the interaction between the promoter and the active phase are briefly highlighted. Advances in developing bifunctional catalysts capable of catalyzing both CO hydrogenation to heavier hydrocarbons and hydrocracking/isomerization of heavier hydrocarbons are critically reviewed. It is demonstrated that the control of the secondary hydrocracking reactions by using core-shell nanostructures or solid-acid materials, such as mesoporous zeolites and carbon nanotubes with acid functional groups, is an effective strategy to tune the product selectivity of Fischer-Tropsch synthesis. Very promising selectivities to gasoline- and diesel-range hydrocarbons have been attained over some bifunctional catalysts. PMID:24339240

  9. Dissection of an antibody-catalyzed reaction.

    OpenAIRE

    Stewart, J D; Krebs, J F; Siuzdak, G; Berdis, A J; Smithrud, D B; Benkovic, S J

    1994-01-01

    Antibody 43C9 accelerates the hydrolysis of a p-nitroanilide by a factor of 2.5 x 10(5) over the background rate in addition to catalyzing the hydrolysis of a series of aromatic esters. Since this represents one of the largest rate accelerations achieved with an antibody, we have undertaken a series of studies aimed at uncovering the catalytic mechanism of 43C9. The immunogen, a phosphonamidate, was designed to mimic the geometric and electronic characteristics of the tetrahedral intermediate...

  10. Ligand Intermediates in Metal-Catalyzed Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gladysz, John A.

    1999-07-31

    The longest-running goal of this project has been the synthesis, isolation, and physical chemical characterization of homogeneous transition metal complexes containing ligand types believed to be intermediates in the metal-catalyzed conversion of CO/H{sub 2}, CO{sub 2}, CH{sub 4}, and similar raw materials to organic fuels, feedstocks, etc. In the current project period, complexes that contain unusual new types of C{sub x}(carbide) and C{sub x}O{sub y} (carbon oxide) ligands have been emphasized. A new program in homogeneous fluorous phase catalysis has been launched as described in the final report.

  11. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei

    2012-01-01

    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  12. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether

    OpenAIRE

    Andrews, Ian P.; Kwon, Ohyun

    2008-01-01

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethy...

  13. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: SOA Yield and Chemical Composition

    Science.gov (United States)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Qi, Li; Kacarab, Mary; Cocker, David

    2016-04-01

    Aromatic hydrocarbons account for 20%-30% of urban atmospheric VOCs and are major contributors to anthropogenic secondary organic aerosol (SOA). However, prediction of SOA from aromatic hydrocarbons as a function of structure, NOx concentration, and OH radical levels remains elusive. Innovative SOA yield and chemical composition evaluation approaches are developed here to investigate SOA formation from aromatic hydrocarbons. SOA yield is redefined in this work by adjusting the molecular weight of all aromatic precursors to the molecular weight of benzene (Yield'= Yieldi×(MWi/MWBenzene); i: aromatic hydrocarbon precursor). Further, SOA elemental ratio is calculated on an aromatic ring basis rather than the classic mole basis. Unified and unique characteristics in SOA formed from aromatic hydrocarbons with different alkyl groups (varying in carbon number and location on aromatic ring) are explored by revisiting fifteen years of UC Riverside/CE-CERT environmental chamber data on 129 experiments from 17 aromatic precursors at urban region relevant low NOx conditions (HC:NO 11.1-171 ppbC:ppb). Traditionally, SOA mass yield of benzene is much greater than that of other aromatic species. However, when adjusting for molecular weight, a similar yield is found across the 17 different aromatic precursors. More importantly, four oxygens per aromatic ring are observed in the resulting SOA regardless of the alkyl substitutes attached to the ring, which majorly affect H/C ratio in SOA. Therefore, resulting SOA bulk composition from aromatic hydrocarbons can be predicted as C6+nH6+2nO4 (n: alkyl substitute carbon number). Further, the dominating role of the aromatic ring carbons is confirmed by studying the chemical composition of SOA formed from the photooxidation of an aromatic hydrocarbon with a 13C isotopically labeled alkyl carbon. Overall, this study unveils the similarity in SOA formation from aromatic hydrocarbons enhancing the understanding of SOA formation from

  14. Dry reforming of hydrocarbon feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Shah, Yatish T. [Norfolk State University; Gardner, Todd H. [U.S. DOE

    2014-09-25

    Developments in catalyst technology for the dry reforming of hydrocarbon feedstocks are reviewed for methane, higher hydrocarbons and alcohols. Thermodynamics, mechanisms and the kinetics of dry reforming are also reviewed. The literature on Ni catalysts, bi-metallic Ni catalysts and the role of promoters on Ni catalysts is critically evaluated. The use of noble and transitional metal catalysts for dry reforming is discussed. The application of solid oxide and metal carbide catalysts to dry reforming is also evaluated. Finally, various mechanisms for catalyst deactivation are assessed. This review also examines the various process related issues associated with dry reforming such as its application and heat optimization. Novel approaches such as supercritical dry reforming and microwave assisted dry reforming are briefly expanded upon.

  15. Proceedings of hydrocarbon contaminated soils

    International Nuclear Information System (INIS)

    While the 1980s witnessed a concentrated effort toward identifying the scientific concerns associated with hydrocarbon contaminated soils, the 1990s offer the hope that even more reliable solutions, both scientific and regulatory, will emerge. The hope for this transition from problem identification to problems solution is evident in these papers from the 5th Annual Conference on Hydrocarbon Contaminated Soils (formerly called Petroleum Contaminated Soils), as the presentations more clearly reflect the maturation of a rapidly evolving field in the areas of chemical analysis, fate, remediation, public health, and regulatory evaluation. This book attempts to address the multidimensional facets of soil contamination by providing various current general perspectives as well as those from the regulatory and the international communities. Technical information is also provided in specific contamination areas such as diesel fuel, as well as analysis and site assessment, remediation, risk assessment, and management

  16. Catalytic ignition of light hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    K. L. Hohn; C.-C. Huang; C. Cao

    2009-01-01

    Catalytic ignition refers to phenomenon where sufficient energy is released from a catalytic reaction to maintain further reaction without additional extemai heating. This phenomenon is important in the development of catalytic combustion and catalytic partial oxidation processes, both of which have received extensive attention in recent years. In addition, catalytic ignition studies provide experimental data which can be used to test theoretical hydrocarbon oxidation models. For these reasons, catalytic ignition has been frequently studied. This review summarizes the experimental methods used to study catalytic ignition of light hydrocarbons and describes the experimental and theoretical results obtained related to catalytic ignition. The role of catalyst metal, fuel and fuel concentration, and catalyst state in catalytic ignition are examined, and some conclusions are drawn on the mechanism of catalytic ignition.

  17. Hydrocarbon Rocket Technology Impact Forecasting

    Science.gov (United States)

    Stuber, Eric; Prasadh, Nishant; Edwards, Stephen; Mavris, Dimitri N.

    2012-01-01

    Ever since the Apollo program ended, the development of launch propulsion systems in the US has fallen drastically, with only two new booster engine developments, the SSME and the RS-68, occurring in the past few decades.1 In recent years, however, there has been an increased interest in pursuing more effective launch propulsion technologies in the U.S., exemplified by the NASA Office of the Chief Technologist s inclusion of Launch Propulsion Systems as the first technological area in the Space Technology Roadmaps2. One area of particular interest to both government agencies and commercial entities has been the development of hydrocarbon engines; NASA and the Air Force Research Lab3 have expressed interest in the use of hydrocarbon fuels for their respective SLS Booster and Reusable Booster System concepts, and two major commercially-developed launch vehicles SpaceX s Falcon 9 and Orbital Sciences Antares feature engines that use RP-1 kerosene fuel. Compared to engines powered by liquid hydrogen, hydrocarbon-fueled engines have a greater propellant density (usually resulting in a lighter overall engine), produce greater propulsive force, possess easier fuel handling and loading, and for reusable vehicle concepts can provide a shorter turnaround time between launches. These benefits suggest that a hydrocarbon-fueled launch vehicle would allow for a cheap and frequent means of access to space.1 However, the time and money required for the development of a new engine still presents a major challenge. Long and costly design, development, testing and evaluation (DDT&E) programs underscore the importance of identifying critical technologies and prioritizing investment efforts. Trade studies must be performed on engine concepts examining the affordability, operability, and reliability of each concept, and quantifying the impacts of proposed technologies. These studies can be performed through use of the Technology Impact Forecasting (TIF) method. The Technology Impact

  18. Catalytic method for synthesizing hydrocarbons

    Science.gov (United States)

    Sapienza, Richard S.; Sansone, Michael J.; Slegeir, William A. R.

    1984-01-01

    A method for synthesizing hydrocarbons from carbon monoxide and hydrogen by contacting said gases with a slurry of a catalyst composed of palladium or platinum and cobalt supported on a solid phase is disclosed. The catalyst is prepared by heating a heterogeneous component of the palladium or platinum deposited on the solid support in a solution of cobalt carbonyl or precursors thereof. The catalyst exhibits excellent activity, stability in air, and produces highly desirable product fractions even with dilute gaseous reactants.

  19. Biodegradation of Polycyclic Aromatic Hydrocarbons

    OpenAIRE

    DEMİR, İsmail; DEMİRBAĞ, Zihni

    1999-01-01

    Polycylic aromatic hydrocarbons (PAHs), such as petroleum and petroleum derivatives, are widespread organic pollutants entering the environment, chiefly, through oil spills and incomplete combustion of fossil fuels. Since most PAHs are persist in the environment for a long period of time and bioaccumulate, they cause environmental pollution and effect biological equilibrium dramatically. Biodegradation of some PAHs by microorganisms has been biochemically and genetically investigated. Ge...

  20. Deep desulfurization of hydrocarbon fuels

    Science.gov (United States)

    Song, Chunshan; Ma, Xiaoliang; Sprague, Michael J.; Subramani, Velu

    2012-04-17

    The invention relates to processes for reducing the sulfur content in hydrocarbon fuels such as gasoline, diesel fuel and jet fuel. The invention provides a method and materials for producing ultra low sulfur content transportation fuels for motor vehicles as well as for applications such as fuel cells. The materials and method of the invention may be used at ambient or elevated temperatures and at ambient or elevated pressures without the need for hydrogen.

  1. Synthesis gas conversion to ethanol and other alcohols catalyzed by cobalt carbonyl

    Energy Technology Data Exchange (ETDEWEB)

    Fahey, D.R.

    1980-08-01

    The threat of diminishing oil and gas feedstocks is forcing us to turn to alternative raw materials for chemicals and fuels production. With vast reserves in the United States and a relative ease of recovery, coal stands fall among the candidate raw-material substitutes. Furthermore, there exists proven technology for the partial oxidation of coal to synthesis gas (a mixture of carbon monoxide and hydrogen) which in turn can be transformed over catalysts into chemicals and fuels. With the exceptions of methanol and methane production, synthesis gas conversions over traditional heterogeneous catalysts yield a complex mixture of hydrocarbon and oxygenated hydrocarbon products (Fischer-Tropsh synthesis). Because of its complexity, this product mixture is more useful as a refinery feedstock than in chemicals production. Homogeneous catalysts often are capable of performing highly selective chemical transformations, so they would appear to offer potential for chemicals production from synthesis gas. Yet this area has been virtually ignored until only very recently. Of the recent reports, the most outstanding example is the rhodium-catalyzed ethylene glycol synthesis. Cobalt is also active for homogeneous catalysis of synthesis gas conversion, and its use for alcohols synthesis is now described.

  2. Polycyclic aromatic hydrocarbon molecules in astrophysics

    Science.gov (United States)

    Rastogi, Shantanu; Pathak, Amit; Maurya, Anju

    2013-06-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are responsible for the mid-infrared emission features. Their ubiquitous presence in almost all types of astrophysical environments and related variations in their spectral profilesmake them an important tool to understand the physics and chemistry of the interstellar medium. The observed spectrum is generally a composite superposition of all different types of PAHs possible in the region. In the era of space telescopes the spectral richness of the emission features has enhanced their importance as probe and also the need to understand the variations with respect to PAH size, type and ionic state. Quantum computational studies of PAHs have proved useful in elucidating the profile variations and put constraints on the possible types of PAHs in different environments. The study of PAHs has also significantly contributed to the problems of diffuse interstellar bands (DIBs), UV extinction and understanding the chemistry of the formation of complex organics in space. The review highlights the results of various computational models for the understanding of infrared emission features, the PAH-DIB relation, formation of prebiotics and possible impact in the understanding of far-infrared features.

  3. Biginelli reaction catalyzed by copper nanoparticles.

    Directory of Open Access Journals (Sweden)

    Manika Dewan

    Full Text Available We recently reported a novel synthesis of copper nanoparticles from copper sulphate utilizing the charge-compensatory effect of ionic liquid [bmim]BF(4 and ethylene glycol. The nanoparticles were characterized and found to be stable for one year. Here we hypothesize that the stabilized nanoparticles should be able to catalyze one-pot multicomponent organic reactions. We show that the nanoparticles catalyzed Biginelli reaction at room temperature to give the product 3,4-dihydopyrimidinone (>90% yield in ~15 minutes from aldehydes, β-diketoester (ethylacetoacetate and urea (or thiourea. . Remarkably, such high yields and rapid kinetics was found to be independent of the electronic density on the reactant aryl-aldehyde. This was probably because even the surface-active particles reacted faster in the presence of ionic liquid as compared to conventional methods. The heterocyclic dihydropyrimidinones (DHPMs and their derivatives are widely used in natural and synthetic organic chemistry due to their wide spectrum of biological and therapeutic properties (resulting from their antibacterial, antiviral, antitumor and anti-inflammatory activities. Our method has an easy work-up procedure and the nanoparticles could be recycled with minimal loss of efficiency.

  4. Palladium-Catalyzed Arylation of Fluoroalkylamines

    Science.gov (United States)

    Brusoe, Andrew T.; Hartwig, John F.

    2015-01-01

    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  5. Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh

    Many biologically active molecules contain one or more nitrogen atoms. Consequently, CN bond formation is a crucial area in the development of pharmaceuticals. The main part of this thesis is devoted to environmentally benign syntheses of different nitrogen scaffolds. Iridium and ruthenium...... tetrafluoroborate as the nitrogen source in reaction with 1,2-cyclohexanediol afforded the morpholine derivative. Finally, attempts to switch to ruthenium catalysis were unsuccessful since neither a RuCl3-PPh3 complex nor a RuCl3-xantphos complex was able to catalyze the reaction between 1,2-diaminocyclohexane and...... ethylene glycol. Mechanistic experiments of the iridium catalyzed reactions revealed that the Voigt isomerization of the α-imino alcohol intermediate to the corresponding α-imino ketone plays a significant role. Synthesis of indoles Anilines and vicinal diols were reacted in the presence of a ruthenium...

  6. Mechanistic Investigation of a Non-Heme Iron Enzyme Catalyzed Epoxidation in (-)-4'-Methoxycyclopenin Biosynthesis.

    Science.gov (United States)

    Chang, Wei-Chen; Li, Jikun; Lee, Justin L; Cronican, Andrea A; Guo, Yisong

    2016-08-24

    Mechanisms have been proposed for α-KG-dependent non-heme iron enzyme catalyzed oxygen atom insertion into an olefinic moiety in various natural products, but they have not been examined in detail. Using a combination of methods including transient kinetics, Mössbauer spectroscopy, and mass spectrometry, we demonstrate that AsqJ-catalyzed (-)-4'-methoxycyclopenin formation uses a high-spin Fe(IV)-oxo intermediate to carry out epoxidation. Furthermore, product analysis on (16)O/(18)O isotope incorporation from the reactions using the native substrate, 4'-methoxydehydrocyclopeptin, and a mechanistic probe, dehydrocyclopeptin, reveals evidence supporting oxo↔hydroxo tautomerism of the Fe(IV)-oxo species in the non-heme iron enzyme catalysis. PMID:27442345

  7. Aminophenols as Efficient Ligand for Copper-Catalyzed Ullmann-type Synthesis of Diaryl Ethers

    International Nuclear Information System (INIS)

    An efficient Cu-catalyzed synthesis of diaryl ethers from various aromatic iodides (bromides) and phenols was developed by using L2(2-((o-toluidino)methyl)phenol) as the ligand. The present protocol is applicable to a variety of phenols and aryl iodides (bromides) containing electron-withdrawing, electron-donating, and sterically demanding substrate combinations under mild conditions. The further study on design and application of new ligands in copper based Ullmann-type coupling reaction is currently ongoing. Carbon-oxygen bonds extensively exist in all kinds of biologically active natural products, important pharmaceutical compounds and polymers. The palladium-catalyzed formation of carbon-oxygen bonds is one of the two major methods available for aryl ether synthesis. However, palladium-based protocols, although successful, have some inherent limitations such as moisture sensitivity, costly metal catalysts, and environmental toxicity

  8. Pd- and Ni-catalyzed cross-coupling reactions in the synthesis of organic electronic materials

    International Nuclear Information System (INIS)

    Organic molecules and polymers with extended π-conjugation are appealing as advanced electronic materials, and have already found practical applications in thin-film transistors, light emitting diodes, and chemical sensors. Transition metal (TM)-catalyzed cross-coupling methodologies have evolved over the past four decades into one of the most powerful and versatile methods for C–C bond formation, enabling the construction of a diverse and sophisticated range of π-conjugated oligomers and polymers. In this review, we focus our discussion on recent synthetic developments of several important classes of π-conjugated systems using TM-catalyzed cross-coupling reactions, with a perspective on their utility for organic electronic materials. (review)

  9. Source rock hydrocarbons. Present status

    International Nuclear Information System (INIS)

    This report first presents the characteristics of conventional oil and gas system, and the classification of liquid and gaseous non conventional hydrocarbons, with the peculiar case of coal-bed methane. The authors then describe how source rock hydrocarbons are produced: production of shale oils and gases (horizontal drilling, hydraulic fracturing, exploitation) and of coal-bed methane and coal mine methane. In the next part, they address and discuss the environmental impact of source rock hydrocarbon production: installation footprint, water resource management, drilling fluids, fracturing fluids composition, toxicity and recycling, air pollution, induced seismicity, pollutions from other exploitation and production activities. They propose an overview of the exploitation and production of source rock gas, coal-bed gas and other non conventional gases in the world. They describe the current development and discuss their economic impacts: world oil context and trends in the USA, in Canada and other countries, impacts on the North American market, on the world oil industry, on refining industries, on the world oil balance. They analyse the economic impacts of non conventional gases: development potential, stakes for the world gas trade, consequence for gas prices, development opportunities for oil companies and for the transport sector, impact on CO2 emissions, macro-economic impact in the case of the USA

  10. Hydrocarbon prospectivity in Western Greece

    Energy Technology Data Exchange (ETDEWEB)

    Maravelis, Angelos; Makrodimitras, George; Zelilidis, Avraam [Patras Univ. (Greece). Lab. of Sedimentology

    2012-06-15

    The geology of Western Greece is dominated by the most external zones of the Hellenide fold-and-thrust belt, namely the Pre-Apulian (or Paxoi) and Ionian zones. With Western Greece and Albania having undergone, in broad terms, similar geological histories, also the hydrocarbon potentials of both areas may be compared. Likewise, the hydrocarbon potential of Italy's Apulian Platform, adjoining in the westerly offshore, may serve as an analogue. Three basin types within Western Greece that deserve hydrocarbon exploration have been examined and are grouped, correlated to major tectonic features, namely foreland (Ionian thrusts' foreland basin), piggy-back (Ionian thrusts' back-arc basin) and strike-slip basins. Additionally, strike-slip basins are further subdivided into the basin north of the Borsh-Khardhiqit strike-slip fault and the Preveza basin, north of Cephalonia transfer fault. Their filling histories suggest the occurrence of Mesozoic carbonate plays and Oligocene/Miocene sandstone plays both for oil and gas.

  11. $100 million for hydrocarbon exploration

    Energy Technology Data Exchange (ETDEWEB)

    Tollinsky, N.

    2009-12-01

    The hydrocarbon and base metal potential of the onshore and offshore segments of the Hudson Platform will be the focus of a $100 million, 5 year study undertaken by the Geological Survey of Canada (GSC) together with the Nunavut, Ontario, Quebec and Manitoba provincial surveys. This geological region encompasses 25 per cent of Canada's landmass. Seventy-five per cent of the budget will be spent in the Canadian Arctic, with the remainder committed to studying the Hudson Platform in Ontario, Quebec and Manitoba. The GSC has stated that although the geoscience information is limited, there are indications that world-class hydrocarbon source rocks are present. Very porous potential reservoir units have been identified. The project will define the basic elements of the hydrocarbon systems in the Hudson and Foxe Basins. According to the thermal conditions in the Hudson Platform, it is probably an oil domain. However, gas may exist in the thicker successions in the northern part of Hudson Bay. The young Devonian rock units in northern Ontario have the potential to eventually generate shallow natural gas called shale gas, a new target that is currently being developed in northern British Columbia. GSC researchers will also study gas escape structures known as pockmarks, discovered during a seafloor mapping program in the northern part of Hudson Bay. The geoscience data will also contribute to land use planning and provide a better understanding on the potential for gas hydrates. 2 refs., 1 fig.

  12. Ethylene Conversion to Higher Hydrocarbon over Copper Loaded BZSM-5 in the Presence of Oxygen

    Institute of Scientific and Technical Information of China (English)

    Ramli Mat; Nor Aishah Saidina Amin; Zainab Ramli; W.Azelee W.Abu Bakar

    2006-01-01

    The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested for ethylene conversion into higher hydrocarbons. The catalytic experiments were carried out in a fixed-bed micro reactor at atmospheric pressure. The catalysts were characterized using XRD, NH3-TPD, and IR for their structure and acidity. The result suggests that BZSM-5 is a weak acid. The introduction of copper into BZSM-5 improved the acidity of BZSM-5. The conversion of ethylene toward higher hydrocarbons is dependent on the acidity of the catalyst. Only weaker acid site is required to convert ethylene to higher hydrocarbons. The loading of Cu on BZSM-5 improved the selectivity for higher hydrocarbons especially at low percentage. The reactivity of ethylene is dependent on the amount of acidity as well as the presence of metal on the catalyst surface. Cu1%BZSM-5 is capable of converting ethylene to higher hydrocarbons. The balances between the metal and acid sites influence the performance of ethylene conversion and higher hydrocarbon selectivity. Higher loading of Cu leads to the formation of COx.

  13. Hydrocarbon- Generating Model of the Area Covered With Volcanic Rock

    Institute of Scientific and Technical Information of China (English)

    Guo Zhanqian; Zhang Yuwei

    2000-01-01

    The distribution of Oil & gas fields shows their close relationship with the most active tectonic regions. This is not a coincidence but having a scientific reasons. The crustal active regions, refer to the places where the active natural earthquake, volcanic activities, underground water happened, and the areas of the leaking off of natural gas to the surface of the crust. The magma of volcanic activities brings the organic "kitchen range body" hydrocarbon- generating model and inorganic genetic hydrocarbon to the regions covered by volcanic rock. Underground water brings a catalytic hydrocarbongenerating model for organic matter, and the leaking- off of H2 and CO2 contributes a synthetic hydrocarbon - generating model. Volcanic activities bring the assemblage of Source, Reservoir and Seal formed by the sediments and magma the sedimentary basins, and the hydrocarbon - generating system with a "water - volcano" binary structure is formed. All these conditions are favorable and excellent for the formation of oil & gas fields. The distribution of American oil & gas fields have very close relationship with the mines of Fe, Mn, Ct, Mo, W and V, deposits of Zn, Cu, V, Pb, Al and Hg, and the deposits of fluorite, sulfur, potassium salt, phosphate and halite, and the distribution of sulfate- chloride of river water. The reason why few oil & gas fields discovered in the regions covered by volcanic rock in western America maybe because of the view of "inconsistency between petroleum and volcano". Further more, It's very difficult to carry out a geophysical exploration in such kinds of regions.This paper examined a few hydrocarbon-generating models (systems) mentioned above and came up with some fresh ideas on the exploration in the areas covered with volcanic rocks.

  14. Power systems utilizing the heat of produced formation fluid

    Science.gov (United States)

    Lambirth, Gene Richard

    2011-01-11

    Systems, methods, and heaters for treating a subsurface formation are described herein. At least one method includes treating a hydrocarbon containing formation. The method may include providing heat to the formation; producing heated fluid from the formation; and generating electricity from at least a portion of the heated fluid using a Kalina cycle.

  15. Hydrocarbon Reserves: Abundance or Scarcity

    International Nuclear Information System (INIS)

    IFP and the OAPEC jointly organize a regular international seminar dealing with world oil-related problems appearing in the news. For the first time, this seminar has been opened to oil and gas company specialists, service companies, research centers and independents. This year's theme concerns oil and gas reserves: are they abundant or are we headed towards the shortages announced by some experts? This theme is especially topical in that: oil and gas currently meet two thirds of world energy needs and almost completely dominate the transport sector; the reserves declared by the OAPEC countries account for nearly half of world reserves; the price of a barrel of oil went through the roof in 2004; world energy demand is growing fast and alternative sources of energy are far from ready to take over from oil and gas in the next few decades. Since the reserves correspond to the volume it is technically and economically viable to produce, the seminar has, of course, dealt with the technical and economic questions that arise in connection with exploration and production, but it has also considered changes in the geopolitical context. Presentations by the leading companies of the OAPEC countries and by the IFP group were completed by presentation from the International Energy Agency (IEA), the United States Geological Survey (USGS), the IHS Energy Group, Total and Gaz de France. This document gathers the transparencies of the following presentations: Hydrocarbon reserves in OAPEC members countries: current and future (M. Al-Lababidi); Non OAPEC liquid reserves and production forecasts (Y. Mathieu); World oil and gas resources and production outlook (K. Chew); Global investments in the upstream (F. Birol); Total's policy in the oil and gas sector (C. de Margerie); Gaz de France's policy in the oil and gas sector (J. Abiteboul); NOC/IOC's opportunities in OPEC countries (I. Sandrea); Relationships between companies, countries and investors: How they may impact on the growth

  16. Hydrocarbon Reserves: Abundance or Scarcity

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2005-07-01

    IFP and the OAPEC jointly organize a regular international seminar dealing with world oil-related problems appearing in the news. For the first time, this seminar has been opened to oil and gas company specialists, service companies, research centers and independents. This year's theme concerns oil and gas reserves: are they abundant or are we headed towards the shortages announced by some experts? This theme is especially topical in that: oil and gas currently meet two thirds of world energy needs and almost completely dominate the transport sector; the reserves declared by the OAPEC countries account for nearly half of world reserves; the price of a barrel of oil went through the roof in 2004; world energy demand is growing fast and alternative sources of energy are far from ready to take over from oil and gas in the next few decades. Since the reserves correspond to the volume it is technically and economically viable to produce, the seminar has, of course, dealt with the technical and economic questions that arise in connection with exploration and production, but it has also considered changes in the geopolitical context. Presentations by the leading companies of the OAPEC countries and by the IFP group were completed by presentation from the International Energy Agency (IEA), the United States Geological Survey (USGS), the IHS Energy Group, Total and Gaz de France. This document gathers the transparencies of the following presentations: Hydrocarbon reserves in OAPEC members countries: current and future (M. Al-Lababidi); Non OAPEC liquid reserves and production forecasts (Y. Mathieu); World oil and gas resources and production outlook (K. Chew); Global investments in the upstream (F. Birol); Total's policy in the oil and gas sector (C. de Margerie); Gaz de France's policy in the oil and gas sector (J. Abiteboul); NOC/IOC's opportunities in OPEC countries (I. Sandrea); Relationships between companies, countries and investors: How they may

  17. Hydrocarbon generation conditions and exploration potential of the Taoudeni Basin, Mauritania

    Institute of Scientific and Technical Information of China (English)

    Gang Wenzhe

    2009-01-01

    The Taoudeni Basin is a typical and steady intracratonic basin in Mauritania, northwest Africa. There are six sets of potential source rocks and five regional unconformable surfaces of the Infracambrian and Paleozoic developed in the basin. We used seismic stratigraphic correlation to recover the denudation thickness of formations at a particular well location. Studies of the hydrocarbon generation history of the basin illustrate that hydrocarbon migration and accumulation occurred in the end of the Carboniferous, and after that, the whole basin suffered denudation for a long period of time. Because there is no thick Mesozoic overburden in the basin, the Silurian source rocks could not generate hydrocarbon in the Mesozoic era for the second time. Consequently, the prospects for successful hydrocarbon exploration in the basin are not good.

  18. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Energy Technology Data Exchange (ETDEWEB)

    Jaars, K.; Beukes, J. P.; van Zyl, P. G.; Venter, A. D.; Josipovic, M.; Pienaar, J. J.; Vakkari, Ville; Aaltonen, H.; Laakso, H.; Kulmala, M.; Tiitta, P.; Guenther, Alex B.; Hellen, H.; Laakso, L.; Hakola, H.

    2014-07-11

    Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol that affect human health, crop production and regional climate. Measurements were conducted at the Welgegund measurement station (South Africa) that is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (>10 million people), the Vaal Triangle (e.g. petrochemical and industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for one year. Samples were collected twice a week for two hours during daytime and two hours 1 during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass 2 selective detector was used for sample preparation and analysis. Results indicated that the 3 monthly median total aromatic hydrocarbon concentrations ranged between 0.01 to 3.1 ppb. 4 Benzene levels did not exceed local air quality standards. Toluene was the most abundant 5 species, with an annual median concentration of 0.63 ppb. No statistically significant 6 differences in the concentrations measured during daytime and night-time were found and no distinct seasonal patterns were observed. Air mass back trajectory analysis proved that the lack of seasonal cycles could be

  19. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Directory of Open Access Journals (Sweden)

    K. Jaars

    2014-02-01

    Full Text Available Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol that affect human health, crop production and regional climate. Measurements were conducted at the Welgegund measurement station (South Africa that is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters, the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters, the Johannesburg–Pretoria metropolitan conurbation (>10 million people, the Vaal Triangle (e.g. petrochemical and pyrometallurgical industries, the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for one year. Samples were collected twice a week for two hours during daytime and two hours during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass selective detector was used for sample preparation and analysis. Results indicated that the monthly median total aromatic hydrocarbon concentrations ranged between 0.01 to 3.1 ppb. Benzene levels did not exceed local air quality standards. Toluene was the most abundant species, with an annual median concentration of 0.63 ppb. No statistically significant differences in the concentrations measured during daytime and night-time were found and no distinct seasonal patterns were observed. Air mass back trajectory analysis proved that the lack of seasonal

  20. Enhanced characterization of reservoir hydrocarbon components using electromagnetic data attributes

    KAUST Repository

    Katterbauer, Klemens

    2015-12-23

    Advances in electromagnetic imaging techniques have led to the growing utilization of this technology for reservoir monitoring and exploration. These exploit the strong conductivity contrast between the hydrocarbon and water phases and have been used for mapping water front propagation in hydrocarbon reservoirs and enhancing the characterization of the reservoir formation. The conventional approach for the integration of electromagnetic data is to invert the data for saturation properties and then subsequently use the inverted properties as constraints in the history matching process. The non-uniqueness and measurement errors may however make this electromagnetic inversion problem strongly ill-posed, leading to potentially inaccurate saturation profiles. Another limitation of this approach is the uncertainty of Archie\\'s parameters in relating rock conductivity to water saturation, which may vary in the reservoir and are generally poorly known. We present an Ensemble Kalman Filter framework for efficiently integrating electromagnetic data into the history matching process and for simultaneously estimating the Archie\\'s parameters and the variance of the observation error of the electromagnetic data. We apply the proposed framework to a compositional reservoir model. We aim at assessing the relevance of EM data for estimating the different hydrocarbon components of the reservoir. The experimental results demonstrate that the individual hydrocarbon components are generally well matched, with nitrogen exhibiting the strongest improvement. The estimated observation error standard deviations are also within expected levels (between 5 and 10%), significantly contributing to the robustness of the proposed EM history matching framework. Archie\\'s parameter estimates approximate well the reference profile and assist in the accurate description of the electrical conductivity properties of the reservoir formation, hence leading to estimation accuracy improvements of around

  1. Synthetic applications of gold-catalyzed ring expansions

    Directory of Open Access Journals (Sweden)

    Cristina Nevado

    2011-06-01

    Full Text Available The development of new methodologies catalyzed by late transition metals involving cycloisomerizations of strained rings can open new venues for the synthesis of structurally complex molecules with interesting biological activities. Herein we summarize, from both a synthetic as well as a mechanistic point of view, the most recent developments in gold-catalyzed ring expansions.

  2. Hydrolysis of toxic natural glucosides catalyzed by cyclodextrin dicyanohydrins

    DEFF Research Database (Denmark)

    Bjerre, J.; Nielsen, Erik Holm Toustrup; Bols, M.

    2008-01-01

    The hydrolysis of toxic 7-hydroxycoumarin glucosides and other aryl and alkyl glucosides, catalyzed by modified a- and ß-cyclodextrin dicyanohydrins, was investigated using different UV, redox, or HPAEC detection assays. The catalyzed reactions all followed Michaelis-Menten kinetics, and an...

  3. The renaissance of palladium(II)-catalyzed oxidation chemistry

    OpenAIRE

    Sigman, Matthew S.; Schultz, Mitchell J.

    2004-01-01

    Palladium(II)-catalyzed oxidations constitute a paramount reaction class but have remained immature over the past few decades. Recently, this field has reappeared at the forefront of organometallic catalysis. This emerging area article outlines recent developments in palladium(II)-catalyzed oxidation chemistry with discussion of potential future growth.

  4. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...

  5. Conversion of natural gas to C2 hydrocarbons through dielectric-barrier discharge plasma catalysis

    Institute of Scientific and Technical Information of China (English)

    王保伟; 许根慧

    2002-01-01

    The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 mL@min?1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons is 76%, and the total selectivity of C2 hydrocarbons and C3 hydrocarbons is nearly 100%. The conversion of methane increases with the increase of voltage and decreases with the flow of methane increase; the selectivity of C2 hydrocarbons decreases with the increase of voltage and increases with the flow of methane increase. The selectivity of C2 hydrocarbons is improved with catalyst for conversion of natural gas to C2 hydrocarbons in plasma field. Methane molecule collision with radicals is mainly responsible for product formation.

  6. Quantifying microbial utilization of petroleum hydrocarbons in salt-marsh sediments using the ^(13)C content of bacterial rRNA

    OpenAIRE

    Pearson, Ann; Kraunz, Kimberly S.; Sessions, Alex L.; Dekas, Anne E.; Leavitt, William R.; Edwards, Katrina J.

    2008-01-01

    Natural remediation of oil spills is catalyzed by complex microbial consortia. Here we take a whole-community approach to investigate bacterial incorporation of petroleum hydrocarbons from a simulated oil spill. We utilized the natural difference in carbon-isotopic abundance between a salt marsh ecosystem supported by the ^(13)C-enriched C4 grass, Spartina alterniflora, and the ^(13)C-depleted composition of petroleum to monitor changes in the ^(13)C content of biomass. Magnetic-bead capture ...

  7. Quantifying Microbial Utilization of Petroleum Hydrocarbons in Salt Marsh Sediments by Using the 13C Content of Bacterial rRNA▿

    OpenAIRE

    Pearson, Ann; Kraunz, Kimberly S.; Sessions, Alex L.; Dekas, Anne E.; Leavitt, William D.; Edwards, Katrina J.

    2007-01-01

    Natural remediation of oil spills is catalyzed by complex microbial consortia. Here we took a whole-community approach to investigate bacterial incorporation of petroleum hydrocarbons from a simulated oil spill. We utilized the natural difference in carbon isotopic abundance between a salt marsh ecosystem supported by the 13C-enriched C4 grass Spartina alterniflora and 13C-depleted petroleum to monitor changes in the 13C content of biomass. Magnetic bead capture methods for selective recovery...

  8. Catalyzed deuterium fueled tandem mirror reactor assessment

    International Nuclear Information System (INIS)

    This study was part of a Department of Energy supported alternate fusion fuels program at Science Applications International Corp. The purpose of this portion of the study is to perform an assessment of a conceptual tandem mirror reactor (TMR) that is fueled by the catalyzed-deuterium (Cat-d) fuel cycle with respect to the physics, technology, safety, and cost. Achievable stable betas and magnet configurations are found to be comparable for the Cat-d and d-t fueled TMR. A comparison with respect to cost, reactor performance, and technology requirements for a Cat-d fueled reactor and a comparable d-t fueled reactor such as MARS is also made

  9. Thioglycoside hydrolysis catalyzed by β-glucosidase

    International Nuclear Information System (INIS)

    Sweet almond β-glucosidase (EC 3.2.1.21) has been shown to have significant thioglycohydrolase activity. While the Km values for the S- and O-glycosides are similar, the kcat values are about 1000-times lower for the S-glycosides. Remarkably, the pH-profile for kcat/Km for hydrolysis of p-nitrophenyl thioglucoside (pNPSG) shows the identical dependence on a deprotonated carboxylate (pKa 4.5) and a protonated group (pKa 6.7) as does the pH-profile for hydrolysis of the corresponding O-glycoside. Not surprisingly, in spite of the requirement for the presence of this protonated group in catalytically active β-glucosidase, thioglucoside hydrolysis does not involve general acid catalysis. There is no solvent kinetic isotope effect on the enzyme-catalyzed hydrolysis of pNPSG

  10. Gallium-Catalyzed Silicon Oxide Nanowire Growth

    Institute of Scientific and Technical Information of China (English)

    Zheng Wei Pan; Sheng Dai; Douglas H.Lowndes

    2005-01-01

    Silicon oxide nanowires tend to assemble into various complex morphologies through a metalcatalyzed vapor-liquid-solid (VLS) growth process. This article summarizes our recent efforts in the controlled growth of silicon oxide nanowire assemblies by using molten gallium as the catalyst and silicon wafer,SiO powder, or silane (SiH4) as the silicon sources. Silicon oxide nanowire assemblies with morphologies of carrotlike, cometlike, gourdlike, spindlelike, badmintonlike, sandwichlike, etc. were obtained. Although the morphologies of the nanowire assemblies are temperature- and silicon source-dependent, they share similar structural and compositional features: all the assemblies contain a microscale spherical liquid Ga ball and a highly aligned, closely packed amorphous silicon oxide nanowire bunch. The Ga-catalyzed silicon oxide nanowire growth reveals several interesting new nanowire growth phenomena that expand our knowledge of the conventional VLS nanowire growth mechanism.

  11. Direct conversion of muon catalyzed fusion energy

    International Nuclear Information System (INIS)

    In this paper a method of direct conversion of muon catalyzed fusion (MCF) energy is proposed in order to reduce the cost of muon production. This MCF concept is based on a pellet composed of many thin solid deuterium-tritium (DT) rods encircled by a metallic circuit immersed in a magnetic field. The direct energy conversion is the result of the heating of the pellet by beam injection and fusion alphas. The expanding DT rods causes the change of magnetic flux linked by the circuit. Our calculation shows that the direct conversion method reduces the cost of one muon by a factor of approximately 2.5 over the previous methods. The present method is compatible with a reactor using the pellet concept, where the muon sticking is reduced by the ion cyclotron resonance heating and the confinement of the exploding pellet is handled by magnetic fields and the coronal plasma. 17 refs., 6 figs

  12. EVALUATION OF PETROLEUM HYDROCARBONS ELUTION FROM SOIL

    OpenAIRE

    Janina Piekutin

    2015-01-01

    The paper presents studies on oil removal from soil by means of water elution with a help of shaking out the contaminants from the soil. The tests were performed on simulated soil samples contaminated with a mixture of petroleum hydrocarbons. The study consisted in recording the time influence and the number of elution cycles to remove contaminants from the soil. The samples were then subject to the determination of petroleum hydrocarbons, aliphatic hydrocarbons, and BTEX compounds (benzene, ...

  13. Statistical Method of Estimating Nigerian Hydrocarbon Reserves

    OpenAIRE

    Jeffrey O. Oseh; Ifeanyi A. Oguamah; Charles U.Omohimoria; Omotara O. Oluwagbenga

    2015-01-01

    Hydrocarbon reserves are basic to planning and investment decisions in Petroleum Industry. Therefore its proper estimation is of considerable importance in oil and gas production. The estimation of hydrocarbon reserves in the Niger Delta Region of Nigeria has been very popular, and very successful, in the Nigerian oil and gas industry for the past 50 years. In order to fully estimate the hydrocarbon potentials in Nigerian Niger Delta Region, a clear understanding of the reserve geology and...

  14. Selective coupling reaction between 2,6-diiodoanisoles and terminal alkynes catalyzed by Pd(PPh32Cl2 and CuI

    Directory of Open Access Journals (Sweden)

    Allan F. C. Rossini

    2012-06-01

    Full Text Available The cross-coupling reaction between aryl halides and terminal alkynes, catalyzed by palladium complexes and copper (I salts, consists in an efficient synthetic tool for the formation of C-C bonds, resulting in disubstituted acetylenic compounds. Accordingly, in this work we present our preliminary results involving the selective cross-coupling reaction between 2,6-diiodoanisoles and terminal alkynes, catalyzed by Pd(PPh32Cl2 and CuI, in the formation of 2-iodo-alkynylanisoles (scheme 1.

  15. Enzyme-catalyzed degradation of carbon nanomaterials

    Science.gov (United States)

    Kotchey, Gregg P.

    Carbon nanotubes and graphene, the nanoscale sp 2 allotropes of carbon, have garnered widespread attention as a result of their remarkable electrical, mechanical, and optical properties and the promise of new technologies that harness these properties. Consequently, these carbon nanomaterials (CNMs) have been employed for diverse applications such as electronics, sensors, composite materials, energy conversion devices, and nanomedicine. The manufacture and eventual disposal of these products may result in the release of CNMs into the environment and subsequent exposure to humans, animals, and vegetation. Given the possible pro-inflammatory and toxic effects of CNMs, much attention has been focused on the distribution, toxicity, and persistence of CNMs both in living systems and the environment. This dissertation will guide the reader though recent studies aimed at elucidating fundamental insight into the persistence of CNMs such as carbon nanotubes (CNTs) and graphene derivatives (i.e., graphene oxide and reduced graphene oxide). In particular, in-testtube oxidation/degradation of CNMs catalyzed by peroxidase enzymes will be examined, and the current understanding of the mechanisms underlying these processes will be discussed. Finally, an outlook of the current field including in vitro and in vivo biodegradation experiments, which have benefits in terms of human health and environmental safety, and future directions that could have implications for nanomedical applications such as imaging and drug delivery will be presented. Armed with an understanding of how and why CNMs undergo enzyme-catalyzed oxidation/biodegradation, researchers can tailor the structure of CNMs to either promote or inhibit these processes. For example, in nanomedical applications such as drug delivery, the incorporation of carboxylate functional groups could facilitate biodegradation of the nanomaterial after delivery of the cargo. Also, the incorporation of CNMs with defect sites in consumer

  16. Enzyme-catalyzed Sequential Reduction of Carbon Dioxide to Formaldehyde☆

    Institute of Scientific and Technical Information of China (English)

    Wenfang Liu; Yanhui Hou; Benxiang Hou; Zhiping Zhao

    2014-01-01

    It has been reported that enzymatic-catalyzed reduction of CO2 is feasible. Most of literature focuses on the con-version of CO2 to methanol. Herein we put emphasis on the sequential conversion of CO2 to formaldehyde and its single reactions. It appears that CO2 pressure plays a critical role and higher pressure is greatly helpful to form more HCOOH as well as HCHO. The reverse reaction became severe in the reduction of CO2 to formaldehyde after 10 h, decreasing HCHO production. Increasing the mass ratio of formate dehydrogenase to formaldehyde dehydrogenase could promote the sequential reaction. At concentrations of nicotinamide adenine dinucleotide lower than 100 mmol·L−1, the reduction of CO2 was accelerated by increasing cofactor concentration. The opti-mum pH value and concentration of phosphate buffer were determined as 6.0 and 0.05 mol·L−1, respectively, for the overall reaction. It seems that thermodynamic factor such as pH is restrictive to the sequential reaction due to distinct divergence in appropriate pH range between its single reactions.

  17. Cobalt-Catalyzed Vinylation of Organozinc Reagents with Aldehydes

    Institute of Scientific and Technical Information of China (English)

    WANG; JinXian

    2001-01-01

    Transtion metal catalyzed vinylation of organic halides are known to be a very convenient method for forming carbon-carbon bonds at unsubstituted vinylic position. The versatility of stilbenes is well known because of its various biological active components, the variety of its reactions in organic syntheses, and its ability to function as a bonding partner for metals in complexes.  Many methods have been described for the synthesis of stilbenes. The reduction, dehydrogenation, and elimination reactions leading to stilbenes without formation of new carbon-carbon bonds are known to be a very convenient methods. Synthetically more important are the dimerization reactions: oxidative or eleminative dimerization of a suitable methylarene often constitutes the method of choice for the preparation of a symmetric stilbene. Meerwein arylation and Heck reaction are prominent examples for the synthesis of stilbenes from arenes and styrenes. Moreover, condensation reactions of a nucleophilic with an electrophilic arylmethyl compound include Knoevenagel type reactions and the very general Wittig and Wittig-Horner reactions are also known methods.  ……

  18. Detection of hydrocarbons in irradiated foods

    Energy Technology Data Exchange (ETDEWEB)

    Miyahara, Makoto; Maitani, Tamio [National Inst. of Health Sciences, Tokyo (Japan); Saito, Akiko; Kamimura, Tomomi; Nagasawa, Taeko [Kitasato Univ., Sagamihara, Kanagawa (Japan). School of Allied Health Sciences; Kobayashi, Yasuo; Ito, Hitoshi [Japan Atomic Energy Research Inst., Takasaki, Gunma (Japan). Takasaki Radiation Establishment

    2003-06-01

    The hydrocarbon method for the detection of irradiated foods is now recognized as the international technique. This method is based on radiolysis of fatty acids in food to give hydrocarbons. In order to expand this technique's application, ten foods (butter, cheese, chicken, pork, beef, tuna, dry shrimp, avocado, papaya, and mango) were irradiated in the range from 0.5 to 10 kGy and the hydrocarbons in them were detected. Recoveries of the hydrocarbons from most foods were acceptable (38-128%). Some hydrocarbons were found in non-irradiated foods, particularly, in butter, cheese, tuna, and shrimp. Seven irradiated foods, butter, cheese, chicken, beef, pork, tuna, dry shrimp, and avocado were detectable at their practical doses by measuring the appropriate marker hydrocarbons. In most case, marker hydrocarbon will be 1,7-hexadecadiene. However, the marker hydrocarbons produced only in irradiated foods varied from food to food; therefore, it is necessary to check a specific irradiated food for marker hydrocarbons. On the other hand, two irradiated foods (papaya and mango which were irradiated at their practical doses) were difficult to distinguish from non-irradiated foods using this method. (author)

  19. Detection of hydrocarbons in irradiated foods

    International Nuclear Information System (INIS)

    The hydrocarbon method for the detection of irradiated foods is now recognized as the international technique. This method is based on radiolysis of fatty acids in food to give hydrocarbons. In order to expand this technique's application, ten foods (butter, cheese, chicken, pork, beef, tuna, dry shrimp, avocado, papaya, and mango) were irradiated in the range from 0.5 to 10 kGy and the hydrocarbons in them were detected. Recoveries of the hydrocarbons from most foods were acceptable (38-128%). Some hydrocarbons were found in non-irradiated foods, particularly, in butter, cheese, tuna, and shrimp. Seven irradiated foods, butter, cheese, chicken, beef, pork, tuna, dry shrimp, and avocado were detectable at their practical doses by measuring the appropriate marker hydrocarbons. In most case, marker hydrocarbon will be 1,7-hexadecadiene. However, the marker hydrocarbons produced only in irradiated foods varied from food to food; therefore, it is necessary to check a specific irradiated food for marker hydrocarbons. On the other hand, two irradiated foods (papaya and mango which were irradiated at their practical doses) were difficult to distinguish from non-irradiated foods using this method. (author)

  20. Commercial valuation of hydrocarbon resources

    International Nuclear Information System (INIS)

    A practical business process is described which enables all categories of hydrocarbon resources to be valued in a commercially consistent manner. The benefits of the process are increased if there is a transparent corporate strategic plan which can be used to test the value of a resource against a desired portfolio, described quantitatively in terms of value and risk. Individual opportunities for both acquisition and disposal can then be measured against an assessed ''Corporate preference profile'' and pursued with increased confidence in the overall fit