WorldWideScience

Sample records for catalyzed hydrocarbon formation

  1. Zeolite-Catalyzed Hydrocarbon Formation from Methanol: Density Functional Simulations

    Directory of Open Access Journals (Sweden)

    George Fitzgerald

    2002-04-01

    Full Text Available Abstract: We report detailed density functional theory (DFT calculations of important mechanisms in the methanol to gasoline (MTG process in a zeolite catalyst. Various reaction paths and energy barriers involving C-O bond cleavage and the first C-C bond formation are investigated in detail using all-electron periodic supercell calculations and recently developed geometry optimization and transition state search algorithms. We have further investigated the formation of ethanol and have identified a different mechanism than previously reported [1], a reaction where water does not play any visible role. Contrary to recent cluster calculations, we were not able to find a stable surface ylide structure. However, a stable ylide structure built into the zeolite framework was found to be possible, albeit a very high reaction barrier.

  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. Formation of hydrocarbons by bacteria and algae

    Energy Technology Data Exchange (ETDEWEB)

    Tornabene, T.G.

    1980-12-01

    A literature review has been performed summarizing studies on hydrocarbon synthesis by microorganisms. Certain algal and bacterial species produce hydrocarbons in large quantities, 70 to 80% of dry cell mass, when in a controlled environment. The nutritional requirements of these organisms are simple: CO/sub 2/ and mineral salts. The studies were initiated to determine whether or not microorganisms played a role in petroleum formation. 90 references. (DMC)

  5. Cogeneration systems and processes for treating hydrocarbon containing formations

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX); Fowler, Thomas David (Houston, TX); Karanikas, John Michael (Houston, TX)

    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. Mechanism of Silurian Hydrocarbon Pool Formation in the Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    Liu Luofu; Guo Yongqiang; Zhao Yande; Li Yan; Chen Yuanzhuang; Chen Lixin; Pang Xiongqi; Xie Qilai; Huo Hong; Zhao Suping; Li Chao; Li Shuangwen

    2007-01-01

    There are three formation stages of Silurian hydrocarbon pools in the Tarim Basin. The widely distributed asphaltic sandstones in the Tazhong (central Tarim) and Tabei (northern Tarim) areas are the results of destruction of hydrocarbon pools formed in the first-stage, and the asphaltic sandstones around the Awati Sag were formed in the second-stage. The hydrocarbon migration characteristics reflected by the residual dry asphalts could represent the migration characteristics of hydrocarbons in the Silurian paleo-pools, while the present movable oil in the Silurian reservoirs is related to the later-stage (the third-stage) hydrocarbon accumulation.

  7. 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

  8. Experimental Probing on Formation Mechanism of Hydrocarbon in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    Weng Kenan; Xiao Wansheng; Zhang Huizi; Wang Benshan

    1997-01-01

    @@ In order to study the formation mechanism of hydrocarbon in the earth's interior, preliminary experiments on chemical reactions of wax, graphite, siderite with supercritical water have been carried out respectively under the conditions of temperature about 800~1500℃ and pressure approximately above 1 GPa. These reactions can produce a large amount of methane, together with some CO2 and a little other hydrocarbons, indicating that the reactions of carbon-bearing materials with supercritical water is possibly a new formation mechanism of hydrocarbon under the conditions of high temperature and high pressure in deep earth.

  9. 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...

  10. 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

  11. 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.

  12. 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....

  13. 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

  14. Formation History of Polycyclic Aromatic Hydrocarbons in Galaxies

    CERN Document Server

    Seok, Ji Yeon; Asano, Ryosuke S

    2014-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are some of the major dust components in the interstellar medium (ISM). We present our evolution models for the abundance of PAHs in the ISM on a galaxy-evolution timescale. We consider shattering of carbonaceous dust grains in interstellar turbulence as the formation mechanism of PAHs while the PAH abundance can be reduced by coagulation onto dust grains, destruction by supernova shocks, and incorporation into stars. We implement these processes in a one-zone chemical evolution model to obtain the evolution of the PAH abundance in a galaxy. We find that PAH formation becomes accelerated above certain metallicity where shattering becomes efficient. For PAH destruction, while supernova shock is the primary mechanism in the metal-poor environment, coagulation is dominant in the metal-rich environment. We compare the evolution of the PAH abundances in our models with observed abundances in galaxies with a wide metallicity range. Our models reproduce both the paucity of PAH...

  15. 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.

  16. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. MINERALIZATION OF A SORBED POLYCYCLIC AROMATIC HYDROCARBON IN TWO SOILS USING CATALYZED HYDROGEN PEROXIDE. (R826163)

    Science.gov (United States)

    Hydrogen peroxide (H2O2) catalyzed by soluble iron or naturally occurring soil minerals, (i.e., modified Fenton's reagent) was investigated as a basis for mineralizing sorbed and NAPL-phase benzo[a]pyrene (BaP), a hydrophobic and toxic polycyclic a...

  19. Silica nanospheres formation induced by peroxidase-catalyzed phenol polymerization

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    To examine whether lignin-like compound is correlated with silica precipitation in grass, a series of simulated chemical experiments were carried out at ambient temperature and pressure, close to cell wall pH, with phenol polymerization catalyzed by peroxidase in silicon solution. The experiments showed that phenol polymer (a kind of lignin-like substance) caused silica nanosphere precipitation similar to those caused by protein in diatom cell wall previously reported by other authors. The sphere diameter varied with different kinds of phenol and the concentrations of phenol and silicon. Silicon precipitation had phenol and silicon saturation effect, meaning that when the concentration ratio of soluble silicon to phenol exceeded a certain value, the amount of silicon precipitation would decrease.

  20. 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.

  1. 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.

  2. 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.

  3. 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-...

  4. 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.

  5. 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

  6. 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.

  7. Stem cells catalyze cartilage formation by neonatal articular chondrocytes in 3D biomimetic hydrogels

    Science.gov (United States)

    Lai, Janice H.; Kajiyama, Glen; Smith, Robert Lane; Maloney, William; Yang, Fan

    2013-12-01

    Cartilage loss is a leading cause of disability among adults and effective therapy remains elusive. Neonatal chondrocytes (NChons) are an attractive allogeneic cell source for cartilage repair, but their clinical translation has been hindered by scarce donor availability. Here we examine the potential for catalyzing cartilage tissue formation using a minimal number of NChons by co-culturing them with adipose-derived stem cells (ADSCs) in 3D hydrogels. Using three different co-culture models, we demonstrated that the effects of co-culture on cartilage tissue formation are dependent on the intercellular distance and cell distribution in 3D. Unexpectedly, increasing ADSC ratio in mixed co-culture led to increased synergy between NChons and ADSCs, and resulted in the formation of large neocartilage nodules. This work raises the potential of utilizing stem cells to catalyze tissue formation by neonatal chondrocytes via paracrine signaling, and highlights the importance of controlling cell distribution in 3D matrices to achieve optimal synergy.

  8. 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)

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

    Energy Technology Data Exchange (ETDEWEB)

    Goldberg, Bernard (Houston, TX); Hale, Arthur Herman (Houston, TX); Miller, David Scott (Katy, TX); Vinegar, Harold J. (Bellaire, TX)

    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.

  10. 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.

  11. Main controlling factors for hydrocarbon reservoir formation and petroleum distribution in Cratonic Area of Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The Cratonic Area of the Tarim Basin is located in the central part of the basin, developing primarily with Cambrian marine source rocks and secondly Middle to Upper Ordovician marine and Carboniferous-Permian transitional facies source rocks. The source rocks were matured in the changeable period and space, forming multiple hydrocarbon generating centers during the periods. The Cratonic Area experienced multiple tectonic orogenies, forming several palaeouplifts. The matching condition between effective hydrocarbon generating centers and the palaeouplifts in various periods is the main control factor for the formation and distribution of hydrocarbon reservoirs. The palaeouplifts have experienced multiple hydrocarbon-filling phases, several periods of modifications and even breakdown. The palaeouplifts and the adjacent slopes around the effective hydrocarbon generating center compose the most favorable places for hydrocarbon accumulation. The hydrocarbon phase is related with the evolution of the hydrocarbon generating center. In the Tarim Basin's Cratonic Area, reservoirs were mostly formed during late Hercynian. The originally formed hydrocarbon reservoirs which are adjacent to source kitchens and in the good preservation condition are the most favorable prospecting targets. Hydrocarbon is richly accumulated under the regional caprock, surrounding the faulted trends, and over and below the unconformity surfaces. Reservoirs in the Carboniferous sandstone, Ordovician karstic weathered crust and carbonate rock inside the buried hill compose the main intervals for hydrocarbon accumulation. Carboniferous and Silurian sandstone pinchout reservoirs and carbonate lithologic reservoirs with rich fractures and pores are the main targets for further prospecting.

  12. 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...

  13. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX); Karanikas, John Michael (Houston, TX); Ryan, Robert Charles (Houston, TX)

    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.

  15. 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

  16. 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...

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. Rate equation approach to understanding the ion-catalyzed formation of peptides

    Science.gov (United States)

    Dubrovskii, V. G.; Sibirev, N. V.; Eliseev, I. E.; Vyazmin, S. Yu; Boitsov, V. M.; Natochin, Yu. V.; Dubina, M. V.

    2013-06-01

    The salt-induced peptide formation is important for assessing and approaching schemes of molecular evolution. Here, we present experimental data and an exactly solvable kinetic model describing the linear polymerization of L-glutamic amino acid in water solutions with different concentrations of KCl and NaCl. The length distributions of peptides are well fitted by the model. Strikingly, we find that KCl considerably enhances the peptide yield, while NaCl does not show any catalytic effect in most cases under our experimental conditions. The greater catalytic effect of potassium ions is entirely interpreted by one and single parameter, the polymerization rate constant that depends on the concentration of a given salt in the reaction mixture. We deduce numeric estimates for the rate constant at different concentrations of the ions and show that it is always larger for KCl. This leads to an exponential increase of the potassium- to sodium-catalyzed peptide concentration ratio with length. Our results show that the ion-catalyzed peptides have a higher probability to emerge in excess potassium rather than in sodium-rich water solutions.

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

    Institute of Scientific and Technical Information of China (English)

    Jerrik Mielby; Raju Poreddy; Christian Engelbrekt; Søren Kegnæs

    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 dehy-drogenation and condensation of alcohols and amines. The reactions were performed under mild conditions and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt%Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H2 in the gas phase. The use of an efficient and selective Ag cata-lyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reac-tion protocol for imine synthesis.

  7. 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...... and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt% Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the 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 Elsevier B...

  8. Forming mechanism of hydrocarbon reservoirs in Yingshan Formation of Yuqi block in Akekule arch, Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    KUANG Li-xiong; GUO Jian-hua; HUANG Tai-zhu

    2008-01-01

    The reservoir conditions, oil and gas charge history and accumulation phases were studied for Yingshan Formation of Yuqi block, and an oil and gas accumulation model was established by using the techniques of reservoir prediction, fluorescence thin section and fluid inclusion analysis under the guidance of the theories of oil and gas accumulation. The results indicate that the main rock types in Yingshan Formation are micrite and calcarenite. The carbonate reservoirs are of cave, fracture-pore and fracture types, and their physical properties are intermediate; there are at least four oil/gas charges, i.e. late Hercynian, Yanshanian, early Himalayan and middle Himalayan (Cenozoic). The most important charge periods are late Hercynian, early Himalayan and middle Himalayan; the oil and gas accumulation model is self source--lateral expulsion of hydrocarbon--multistage accumulation, or hydrocarbon sourced from and preserved in the same old rocks--long term expulsion of hydrocarbon--multistage accumulation.

  9. Formation of phosgene during welding activities in an atmosphere containing chlorinated hydrocarbons.

    Science.gov (United States)

    Nieuwenhuizen, M S; Groeneveld, F R

    2000-01-01

    The formation of phosgene During welding activities in an atmosphere containing chlorinated hydrocarbons was investigated. Four different chlorinated hydrocarbons were studied under laboratory conditions. Results are presented as time-averaged phosgene concentration in a total volume of 250 L of air being purged through a 52-L reaction vessel during 20 min. It was found that the formation of phosgene was in the order dichloromethane smoke particles and because of possible nonhomogeneous dispersion of phosgene around the workers. In the case of dichloromethane and carbon tetrachloride the short-term maximum allowable concentration (MAC) of phosgene was not attained at the respective MAC values of the chlorinated hydrocarbons themselves. In the case of trichloroethylene and Freon-22, however, the short-term MAC-value of phosgene was attained even when the concentration was still much below the respective MAC-values.

  10. 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 (...

  11. 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...

  12. [(NHC)AuI]-catalyzed formation of conjugated enones and enals: an experimental and computational study.

    Science.gov (United States)

    Marion, Nicolas; Carlqvist, Peter; Gealageas, Ronan; de Frémont, Pierre; Maseras, Feliu; Nolan, Steven P

    2007-01-01

    The [(NHC)AuI]-catalyzed (NHC=N-heterocyclic carbene) formation of alpha,beta-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60 degrees C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2' addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C[triple chemical bond]C bond leading to the formation of a gold-allenolate is proposed. PMID:17530724

  13. Kinetics and mechanism of soot formation in hydrocarbon combustion

    Science.gov (United States)

    Frenklach, Michael

    1990-01-01

    The focus of this work was on kinetic modeling. The specific objectives were: detailed modeling of soot formation in premixed flames, elucidation of the effects of fuel structure on the pathway to soot, and the development of a numerical technique for accurate modeling of soot particle coagulation and surface growth. Those tasks were successfully completed and are briefly summarized.

  14. 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.

  15. 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

  16. Normal hydrocarbons as a source of resin formation in the process of obtaining isoprene from isopentane

    Energy Technology Data Exchange (ETDEWEB)

    Isagulyants, G.V.; Sire, Y.M.; Vasil' yeva, V.P.; Gitis, K.M.; Rozengart, M.I.

    1981-01-01

    A study was made on a catalyst of dehydrogenation of olefins of the conversion of isoamylenes and other C/sub 5/ hydrocarbons (isoprene, n-pentenes, piperylene), formed during dehydrogenation of isoamylenes to isoprene. It was found that the yield of heavy products increases on transition from hydrocarbons of iso-structure to normal hydrocarbons, which is due to the greater ease of polycondensation of cyclopentadiene formed from n-pentenes and particularly from piperylene under conditions of dehydrogenation. A study was made by chromato-mass-spectrometry of the composition of heavy products of conversion of piperylene and isoprene. In contrast with the catalysate of isoprene, the catalysate of piperylene contains a significant proportion of hydrocarbons containing a five-membered ring in the molecule (dicyclopentadiene, indane, indene, methylindenes, azilene), this being due to the participation of cyclopentadiene in the formation of heavy products. In the two-stage process of dehydrogenation of isopentane to isoprene 95% normal hydrocarbons are formed on dehydrogenation of isopentane to isoamylenes. (JMT)

  17. 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

  18. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Directory of Open Access Journals (Sweden)

    Ohgi Takahashi

    2015-01-01

    Full Text Available Succinimide formation from aspartic acid (Asp residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe as a model compound, we propose the possibility that acetic acid (AA, which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  19. 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.

  20. 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.

  1. 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...

  2. 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.

  3. 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...

  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. FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

    Science.gov (United States)

    The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

  6. Duration of the hydrocarbon fluid formation under thermobaric conditions of the Earth's upper mantle

    Science.gov (United States)

    Mukhina, Elena; Kolesnikov, Anton; Kutcherov, Vladimir

    2016-04-01

    Deep abiogenic formation of hydrocarbons is an inherent part of the Earth's global carbon cycle. It was experimentally confirmed that natural gas could be formed from inorganic carbon and hydrogen containing minerals at pressure and temperature corresponding to the Earth's upper mantle conditions. Reaction between calcite, wustite and water in the large volume device was studied in several works. It was previously proposed that reaction is possible only after 40 minutes of exposure at high pressure and temperature. In this work similar experiment at P = 60 kbar and T = 1200 K were carried out in "Toroid" type chamber with the 5 seconds duration of thermobaric exposure. Gas chromatographic analysis of the reaction products has shown the presence of hydrocarbon mixture comparable to 5 minutes and 6 hours exposure experiments. Based on this fact it is possible to conclude that the reaction of natural gas formation is instant at least at given thermobaric conditions. This experiment will help to better understand the process of deep hydrocarbon generation, particularly its kinetics.

  7. Hydrocarbons exploration, development from low-permeability chalks - upper cretaceous Niobrara formation, Rocky Mountains region

    Energy Technology Data Exchange (ETDEWEB)

    Pollastro, R.M.; Scholle, P.A.

    1984-04-23

    The Niobrara formation in the Rocky Mountains/Great Plains region serves as a classic model in research, exploration, production, and development programs involving unconventional reservoirs and source-rock systems. Numerous geologic and geochemical studies of the organic and inorganic constituents within the chalk of the Upper Cretaceous Niobrara formation, as well as other chalks and associated units, have identified several depositional and diagenetic relationships, giving explorationists more insight into reservoir properties and hydrocarbon maturity in a particular area of interest. The identification and understanding of the geologic, geophysical, and engineering aspects of these chalks have helped develop the Niobrara into a major play area in the Rocky Mountains/Great Plains region. Geologists, reviewing the area's (1) structural relationships and hydrocarbon distribution, (2) reservoir parameters, (3) production technology and log evaluation, (4) fracture stimulation and production characteristics, and (5) exploration models and resource potential, predict that the Niobrara is a highly promising hydrocarbon reservoir/source-rock system that will make a significant contribution to the energy resources of the Denver basin and adjacent areas.

  8. 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.

  9. Experimental Study on Hydrocarbon Formation Due to Reactions Between Carbonates and Water or Water—Bearing Minerals in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    翁克难; 汪本善; 等

    1999-01-01

    In order to investigate the mechanism of formation of abiogenetic hydrocarbons at the depth of the Earth,experimental research on reactions between carbonates and water or waterbearing minerals was carried out at the pressure of about 1GPa and the temperature range of 800-1500℃.The reactions took place in an open and nonequilibrium state.Chromatographic analyses of the gas products indicate that in the experiments there were generated CH4-dominated hydrocarbons,along with some CO2 and CO.Accordingly,we think there is no essential distinction between free-state water and hydroxy in the minerals in the process of hydrocarbon formation.This study indicates that reactions between carbonates and water or water-bearing minerals should be an important factor leading to the formation of abiogenetic hydrocarbons at the Earth's depth.

  10. On the Role of Carbides in the Formation of Hydrocarbons from Deep Carbon

    Science.gov (United States)

    Vecht, A.

    2012-12-01

    The origin of hydrocarbons found in rocks has been a matter of dispute for over a century. Scientists of the former Soviet Union favoured an inorganic origin, while in the west an organic origin was thought the most likely. Both hypotheses may be reconciled by considering the origin of carbon compounds from the core upwards or from the Earth surface downwards. Carbides are the key to understanding the development and distribution of global carbon compounds. They are precursors in the formation of hydrocarbons. It has been estimated that the Earth's core is composed of between 2-4% carbon. It is found in metallic form and is substantially denser that the surrounding mantle. Wood has proposed that the inner core is a carbide probably iron carbide(1). This conclusion is consistent with studies of meteorites, shock waves and densities Carbides can be divided into four groups:- (a) Interstitial: -Ti, V, Cr, Zr, Nb, Hf, Ta and W. (b) Covalent:- B and Si (c) Intermediate:- Ti, V, Cr, Mn, Fe, Co and Ni. (d) Salt like:- Groups I, II, and III. Groups (a) (b) and (c) should be included as candidates for carbides found in the inner core. Such carbides are stable at high temperature and will react with water and/or oxygen to form hydrocarbons and CO or CO2 respectively., carbides can be described as examples of a 'reactive minerals' as we suggested in 2007(2). Carbides which are stable at high temperatures react with water to yield hydrocarbons. This points to an abiotic origin for a range of natural hydrocarbons. A detailed review by Cataldo(3) analysed the relevant evidence for biological vs. inorganic origins. He suggests that metal carbides when hydrolysed yield organic 'matter'. Amongst the carbides suggested are (Cr, Fe, Ni, V, Mn and Co}. These carbides are correlated to the relative abundance of these elements in the solar system. We propose similar reactions based on carbides of calcium and aluminium for the formation of methane hydrate. The reactions are expected to

  11. 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;

    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......, in agreement with recent IR measurements. Complementary density functional theory calculations confirm the stability of the observed superhydrogenated species toward spontaneous H and H2 loss indicating that abstraction reactions may be the dominant route to H2 formation involving neutral polycyclic aromatic...... hydrocarbons (PAHs). The results indicate that highly superhydrogenated PAHs could well be formed and could act as efficient catalysts for H2 formation in the interstellar medium in low UV flux regions....

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. High-quality hydrocarbon source rock in the Paleogene sequence of the Ping Chau Formation, Hong Kong

    Institute of Scientific and Technical Information of China (English)

    YAO Suping; HU Wenxuan; CHEN Longsheng; ZHU Dongya; XUE Chunyan

    2005-01-01

    Although petroleum exploration is being conducted in the Hong Kong region, high-quality hydrocarbon source rocks have never been found in this area. The Ping Chau Formation is only Mesozoic-Cenozoic sedimentary rock exposed in Hong Kong and its surrounding areas. The hydrocarbon source rock of the Ping Chau Formation is very rich in organic matters, which has an average total organic carbon (TOC) of 1.9% and chloroform bitumen "A" range from 0.14% to 0.24%. The total hydrocarbon content varies from 880 to 1800 ppm and the transformation ratio is spe- cific from 5 to 9. The index of pyrolytic hydrogen is up to about 600 mgHC/gTOC. These data demonstrate the char- acteristics of the high-quality hydrocarbon source rock. The lamalginite is the major maceral of the source rock of the Ping Chau Formation, and geochemical characteristics also suggest that the organic materials of the source rock are of type I and type II1, with abundant gammacerane, γ, β-carotane and C24 tetracyclic terpane, which indicate that it was formed in the salt water and brackish water sedimentary environment, and the source rock has evolved into a mature phase. The organic inclusions are found within calcite veins in cracks of the source rock, indicating that hydrocarbon has been generated and a secondary migration has happened. The source rock in the Ping Chau Formation is about 200-300 m thick, thus having considerable hydrocarbon potential. The discovery of the high quality hydrocarbon source rock in the Ping Chau Formation will certainly provide insight on hydrocarbon resource exploration in the South China Sea area.

  17. 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 determi...

  18. 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.

  19. 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.

  20. 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 ...

  1. Impact of molecular structure on secondary organic aerosol formation from aromatic hydrocarbon photooxidation under low-NOx conditions

    Science.gov (United States)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Cocker, David R., III

    2016-08-01

    The molecular structure of volatile organic compounds determines their oxidation pathway, directly impacting secondary organic aerosol (SOA) formation. This study comprehensively investigates the impact of molecular structure on SOA formation from the photooxidation of 12 different eight- to nine-carbon aromatic hydrocarbons under low-NOx conditions. The effects of the alkyl substitute number, location, carbon chain length and branching structure on the photooxidation of aromatic hydrocarbons are demonstrated by analyzing SOA yield, chemical composition and physical properties. Aromatic hydrocarbons, categorized into five groups, show a yield order of ortho (o-xylene and o-ethyltoluene) > one substitute (ethylbenzene, propylbenzene and isopropylbenzene) > meta (m-xylene and m-ethyltoluene) > three substitute (trimethylbenzenes) > para (p-xylene and p-ethyltoluene). SOA yields of aromatic hydrocarbon photooxidation do not monotonically decrease when increasing alkyl substitute number. The ortho position promotes SOA formation while the para position suppresses aromatic oxidation and SOA formation. Observed SOA chemical composition and volatility confirm that higher yield is associated with further oxidation. SOA chemical composition also suggests that aromatic oxidation increases with increasing alkyl substitute chain length and branching structure. Further, carbon dilution conjecture developed by Li et al. (2016) is extended in this study to serve as a standard method to determine the extent of oxidation of an alkyl-substituted aromatic hydrocarbon.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Comparing gas-phase and grain-catalyzed H2 formation

    CERN Document Server

    Glover, S C O

    2003-01-01

    Because H2 formation on dust grain surfaces completely dominates gas-phase H2 formation in local molecular clouds, it is often assumed that gas-phase formation is never important. In fact, it is the dominant mechanism in a number of cases. In this paper, I briefly summarize the chemistry of gas-phase H2 formation, and show that it dominates for dust-to-gas ratios less than a critical value D_cr. I also show that D_cr is simple to calculate for any given astrophysical situation, and illustrate this with a number of examples, ranging from H2 formation in warm atomic gas in the Milky Way to the formation of protogalaxies at high redshift.

  8. 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

  9. Mechanistic investigation into the formation of polycyclic aromatic hydrocarbons from the pyrolysis of plant steroids

    Energy Technology Data Exchange (ETDEWEB)

    Britt, P.F.; Buchanan, A.C. III; Kidder, M.M.; Owens, C.; Ammann, J.R.; Skeen, J.T.; Luo, L. [Oak Ridge National Lab., Oak Ridge, TN (United States). Chemical and Analytical Sciences

    2001-10-09

    There have been many studies on the pyrolysis of biomass model compounds but most have not been performed under the high heating rate, short residence time conditions currently used in the thermochemical conversion of biomass. In this investigation, the pyrolysis of plant steroids is investigated by flash vacuum pyrolysis (FVP) and flow pyrolysis at residence times of 0.1-2.0 s and temperatures of 550-800{degree}C to determine if the native cyclic ring structure in the steroid leads to the formation of polycyclic aromatic hydrocarbons (PAHs) or whether PAHs are formed by pyrosynthesis. FVP of stigmasterol stigmasterol acetate, {beta}-sitosterol and stigmasta-3,5-diene at 700{degree}C showed that PAHs, such as acenaphthylene, phenanthrene, anthracene, pyrene, chrysene, benz(a)anthracene, and their monomethylated derivatives were formed in the absence of bimolecular reactions, and the yield of PAHs was dependent of the structure of the steroid. Similar products were found in the flow pyrolysis of stigmasterol, and the yields of PAHs were found to increase with increasing temperature and residence time. Thermochemical kinetic estimates were used to postulate pathways for the formation of the primary pyrolysis products. 66 refs., 9 figs., 7 tabs.

  10. EXPERIMENTAL EVIDENCE FOR THE FORMATION OF HIGHLY SUPERHYDROGENATED POLYCYCLIC AROMATIC HYDROCARBONS THROUGH H ATOM ADDITION AND THEIR CATALYTIC ROLE IN H{sub 2} FORMATION

    Energy Technology Data Exchange (ETDEWEB)

    Thrower, J. D.; Jorgensen, B.; Friis, E. E.; Baouche, S.; Luntz, A. C.; Andersen, M.; Hammer, B.; Hornekaer, L. [Department of Physics and Astronomy and Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000 Aarhus C (Denmark); Mennella, V., E-mail: thrower@phys.au.dk [Istituto Nazionale di Astrofisica, Osservatorio Astronomico di Capodimonte, Via Moiariello 16, 80131 Napoli (Italy)

    2012-06-10

    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 H{sub 2} formation, in agreement with recent IR measurements. Complementary density functional theory calculations confirm the stability of the observed superhydrogenated species toward spontaneous H and H{sub 2} loss indicating that abstraction reactions may be the dominant route to H{sub 2} formation involving neutral polycyclic aromatic hydrocarbons (PAHs). The results indicate that highly superhydrogenated PAHs could well be formed and could act as efficient catalysts for H{sub 2} formation in the interstellar medium in low UV flux regions.

  11. 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.

  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......, and the model predicts inception of soot to occur approximately 100 K below experimental observations. Addition of water vapor has a considerable effect on the measured acetylene concentration and on soot formation at 1500 K and above. In this temperature regime, concentrations of both acetylene and soot...

  13. G protein activation by G protein coupled receptors: ternary complex formation or catalyzed reaction?

    Science.gov (United States)

    Roberts, David J; Waelbroeck, Magali

    2004-09-01

    G protein coupled receptors catalyze the GDP/GTP exchange on G proteins, thereby activating them. The ternary complex model, designed to describe agonist binding in the absence of GTP, is often extended to G protein activation. This is logically unsatisfactory as the ternary complex does not accumulate when G proteins are activated by GTP. Extended models taking into account nucleotide binding exist, but fail to explain catalytic G protein activation. This review puts forward an enzymatic model of G protein activation and compares its predictions with the ternary complex model and with observed receptor phenomenon. This alternative model does not merely provide a new set of formulae but leads to a new philosophical outlook and more readily accommodates experimental observations. The ternary complex model implies that, HRG being responsible for efficient G protein activation, it should be as stable as possible. In contrast, the enzyme model suggests that although a limited stabilization of HRG facilitates GDP release, HRG should not be "too stable" as this might trap the G protein in an inactive state and actually hinder G protein activation. The two models also differ completely in the definition of the receptor "active state": the ternary complex model implies that the active state corresponds to a single active receptor conformation (HRG); in contrast, the catalytic model predicts that the active receptor state is mobile, switching smoothly through various conformations with high and low affinities for agonists (HR, HRG, HRGGDP, HRGGTP, etc.).

  14. 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

  15. 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.

  16. Lewis Base-Catalyzed Formation of α-Trifluoromethyl Alcohol from CF3SiMe3 and Carbonyl-Containing Compounds

    Institute of Scientific and Technical Information of China (English)

    ZHU Shi-Fa; PANG Wan; XING Chun-Hui; ZHU Shi-Zheng

    2007-01-01

    Lewis base could catalyze the formation of α-trifluoromethyl alcohol from CF3SiMe3 and carbonyl-containingcompounds. It was found that the a-trilluoromethyl alcohol could also be used to promote the synthesis in basic conditions.

  17. 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 ...

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. 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.)

  5. Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation

    Science.gov (United States)

    2016-01-01

    A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C–C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C–C bonds. PMID:27704805

  6. 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

  7. 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

  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. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation.

    Science.gov (United States)

    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A

    2014-03-10

    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    Science.gov (United States)

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.

  15. Coke Formation in a Zeolite Crystal During the Methanol-to-Hydrocarbons Reaction as Studied with Atom Probe Tomography.

    Science.gov (United States)

    Schmidt, Joel E; Poplawsky, Jonathan D; Mazumder, Baishakhi; Attila, Özgün; Fu, Donglong; de Winter, D A Matthijs; Meirer, Florian; Bare, Simon R; Weckhuysen, Bert M

    2016-09-01

    Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using (13) C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30-60 (13) C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation. PMID:27485276

  16. 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,...

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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;

    1999-01-01

    Diacylglycerols (DAGs) are important intermediates in lipase-catalyzed interesterification, but a high DAG concentration in the reaction mixture results in a high DAG content in the final product. We have previously shown that a high DAG concentration in the reaction mixture increases the degree ...

  2. Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

    Science.gov (United States)

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

    2012-07-24

    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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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.

  11. Surface films of short fluorocarbon-hydrocarbon diblocks studied by molecular dynamics simulations: Spontaneous formation of elongated hemimicelles.

    Science.gov (United States)

    Piñeiro, Angel; Prieto, Gerardo; Ruso, Juan M; Verdes, Pedro V; Sarmiento, Félix

    2009-01-15

    Using grazing incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) it has been recently demonstrated that linear fluorocarbon-hydrocarbon diblocks (FnHm) self-assemble in water/air interfaces forming elongated and circular hemimicelles. Those structures have been observed for diblocks with at least eight fluorinated carbons. Based on the lack of a collapse pressure for F6H16, and due to the fact that no stable surface pressure values are reached under compression, it has been concluded that these molecules do not form stable monolayers. It has been also suggested that F6H16 and shorter diblocks desorb from the water surface under compression. It is not easy to accept that a significant concentration of so hydrophobic molecules can be stable in aqueous solution even when the employed experimental techniques were not able to clearly detect a well defined structure on the interface. In the present work the adsorption and arrangement of F6H16 and F6H10 at the water surface are studied by molecular dynamics (MD) simulations as a function of the available area per molecule. Starting from a random mixture, the spontaneous formation of elongated hemimicelles is observed for both systems when the area per molecule is higher than approximately 50 A(2). For intermediate areas two pseudo-phases, one rich in hydrocarbons and the other with higher fluorocarbon concentration, are formed. For the systems with less than approximately 30 A(2) available per molecule the formation of multilayers is observed. This is the first time that the dynamics and structure of perfluoroalkane (PFA) films, and in particular of hemimicelles on a liquid surface, are observed and characterized at atomic level.

  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. 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

  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 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.

  16. 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

  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. 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).

  20. Acetic acid-catalyzed formation of N-phenylphthalimide from phthalanilic acid: a computational study of the mechanism.

    Science.gov (United States)

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-05-28

    In glacial acetic acid, phthalanilic acid and its monosubstituents are known to be converted to the corresponding phthalimides in relatively good yields. In this study, we computationally investigated the experimentally proposed two-step (addition-elimination or cyclization-dehydration) mechanism at the second-order Møller-Plesset perturbation (MP2) level of theory for the unsubstituted phthalanilic acid, with an explicit acetic acid molecule included in the calculations. In the first step, a gem-diol tetrahedral intermediate is formed by the nucleophilic attack of the amide nitrogen. The second step is dehydration of the intermediate to give N-phenylphthalimide. In agreement with experimental findings, the second step has been shown to be rate-determining. Most importantly, both of the steps are catalyzed by an acetic acid molecule, which acts both as proton donor and acceptor. The present findings, along with those from our previous studies, suggest that acetic acid and other carboxylic acids (in their undissociated forms) can catalyze intramolecular nucleophilic attacks by amide nitrogens and breakdown of the resulting tetrahedral intermediates, acting simultaneously as proton donor and acceptor. In other words, double proton transfers involving a carboxylic acid molecule can be part of an extensive bond reorganization process from cyclic hydrogen-bonded complexes.

  1. 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

  2. Muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, K. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Nagamine, K. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Matsuzaki, T. [Advanced Meson Science Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Kawamura, N. [Muon Science Laboratory, IMSS-KEK, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2005-12-15

    The latest progress of muon catalyzed fusion study at the RIKEN-RAL muon facility (and partly at TRIUMF) is reported. The topics covered are magnetic field effect, muon transfer to {sup 3}He in solid D/T and ortho-para effect in dd{mu} formation.

  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. CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para' C-C Phenol Couple in the Amaryllidaceae Alkaloids

    Science.gov (United States)

    Kilgore, Matthew B.; Augustin, Megan M.; May, Gregory D.; Crow, John A.; Kutchan, Toni M.

    2016-01-01

    The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para', para-ortho', or ortho-para' regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para' C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS)-noroxomaritidine and (10bS,4aR)-noroxomaritidine from 4′-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho' phenol coupled product, N-demethylnarwedine, as less than 1% of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4′-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot. PMID:26941773

  5. CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para’ C-C Phenol Couple in the Amaryllidaceae Alkaloids

    Directory of Open Access Journals (Sweden)

    Matthew eKilgore

    2016-02-01

    Full Text Available The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para’, para-ortho’, or ortho-para’ regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para’ C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS-noroxomaritidine and (10bS,4aR-noroxomaritidine from 4’-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho’ phenol coupled product, N-demethylnarwedine, as less than 1 % of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4’-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot.

  6. 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

  7. Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals.

    Science.gov (United States)

    Guan, Ying-Hong; Ma, Jun; Ren, Yue-Ming; Liu, Yu-Lei; Xiao, Jia-Yue; Lin, Ling-qiang; Zhang, Chen

    2013-09-15

    Magnetic porous copper ferrite (CuFe2O4) showed a notable catalytic activity to peroxymonosulfate (PMS). More than 98% of atrazine was degraded within 15 min at 1 mM PMS and 0.1 g/L CuFe2O4. In contrast, CuFe2O4 exhibited no obvious catalytic activity to peroxodisulfate or H2O2. Several factors affecting the catalytic performance of PMS/CuFe2O4 were investigated. Results showed that the catalytic degradation efficiency of atrazine increased with PMS and CuFe2O4 doses, but decreased with the increase of natural organic matters concentration. The catalytic oxidation also showed a dependence on initial pH. The presence of bicarbonate stimulated atrazine degradation by PMS/CuFe2O4 at low concentrations but inhibited the degradation at high concentrations. Furthermore, the reactive species for atrazine degradation in PMS/CuFe2O4 system were identified as hydroxyl radical (HO) and sulfate radical (SO4(·-)) through competition reactions of atrazine and nitrobenzene, instead of commonly used alcohol scavenging, which was not a reliable method in metal oxide catalyzed oxidation. Surface hydroxyl groups of CuFe2O4 were a critical part in radical generation and the copper on CuFe2O4 surface was an active site to catalyze PMS. The catalytic degradation of atrazine by PMS/CuFe2O4 was also effective under the background of actual waters.

  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. 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.

  10. Model compound study of the pathways for aromatic hydrocarbon formation in soot.

    Energy Technology Data Exchange (ETDEWEB)

    Winans, R. E.; Tomczyk, N. A.; Hunt, J. E.; Solum, M. S.; Pugmire, R. J.; Jiang, Y. J.; Fletcher, T. H.; Univ. of Utah; Brigham Young Univ.

    2007-09-01

    As a follow-up of previous work on the flame pyrolysis of biphenyl and pyrene, a more detailed analysis of the pyrolytic products has been done using additional NMR data obtained on the whole soot sample correlated with detailed high-resolution and GC mass spectrometry data on the solvent-extracted portion of the same samples. These latter data complement the earlier NMR data with details of the pre-sooting structures, referred to as 'young soot', in pyrolyzed biphenyl samples collected at 1365, 1410, and 1470 K and pyrene at 1410 and 1470 K. The data reveal the roles played by free-radical-assisted polymerization reactions as well as the hydrogen-abstraction carbon-addition (HACA) reactions for the biphenyl pyrolysis. The mass spectroscopy data of pyrene describe a much different set of reactions due to polymerization which employs free-radical reactions of the pyrene due primarily to hydrogen abstraction followed by the formation of biaryl linkages at mass numbers up to five times that of the parent pyrene. Conceptual schema of reaction mechanisms are proposed to explain the formation pathways to materials detected in the soot extracts.

  11. Model compound study of the pathways for aromatic hydrocarbon formation in soot

    Energy Technology Data Exchange (ETDEWEB)

    Randall E. Winans; Nancy A. Tomczyk; Jerry E. Hunt; Mark S. Solum; Ronald J. Pugmire; Yi Jin Jiang; Thomas H. Fletcher [University of Utah, Salt Lake City, UT (United States). Department of Chemistry

    2007-07-01

    A previous study was conducted to determine the early sooting pathways of biphenyl and pyrene. Soot/pah samples from biphenyl were collected in a fuel-rich flat-flame burner at temperatures of 1365, 1410, and 1470 K and from pyrene at 1410 and 1470K. A more detailed analysis of the pyrolitic products has been performed using additional NMR data obtained on the whole soot sample correlated with detailed high resolution as well as GC mass spectrometry data on the solvent extracted portion of the same samples. These latter data complement the earlier NMR data with details of the pre-sooting structures, referred to as 'young soot.' The data reveal the roles played by free radical assisted polymerization reactions as well as the hydrogen abstraction carbon addition (HACA) reactions for the biphenyl pyrolysis. The mass spectroscopy data of pyrene describe a much different set of reactions due to polymerization which employs free radical reactions of the pyrene due primarily to hydrogen abstraction followed by the formation of biaryl linkages at mass numbers up to five times that of the parent pyrene. Conceptual schema of reaction mechanisms are proposed to explain the formation pathways to materials detected in the soot extracts. 21 refs., 6 figs., 4 tabs.

  12. Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs low-yield pathways

    Directory of Open Access Journals (Sweden)

    D. K. Henze

    2007-10-01

    Full Text Available Formation of SOA from the aromatic species toluene, xylene, and, for the first time, benzene, is added to a global chemical transport model. A simple mechanism is presented that accounts for competition between low and high-yield pathways of SOA formation, wherein secondary gas-phase products react further with either nitrogen oxide (NO or hydroperoxy radical (HO2 to yield semi- or non-volatile products, respectively. Aromatic species yield more SOA when they react with OH in regions where the [NO]/[HO2] ratios are lower. The SOA yield thus depends upon the distribution of aromatic emissions, with biomass burning emissions being in areas with lower [NO]/[HO2] ratios, and the reactivity of the aromatic with respect to OH, as a lower initial reactivity allows transport away from industrial source regions, where [NO]/[HO2] ratios are higher, to more remote regions, where this ratio is lower and, hence, the ultimate yield of SOA is higher. As a result, benzene is estimated to be the most important aromatic species with regards to formation of SOA, with a total production nearly equal that of toluene and xylene combined. In total, while only 39% percent of the aromatic species react via the low-NOx pathway, 72% of the aromatic SOA is formed via this mechanism. Predicted SOA concentrations from aromatics in the Eastern United States and Eastern Europe are actually largest during the summer, when the [NO]/[HO2] ratio is lower. Global production of SOA from aromatic sources is estimated at 3.5 Tg/yr, resulting in a global burden of 0.08 Tg, twice as large as previous estimates. The contribution of these largely anthropogenic sources to global SOA is still small relative to biogenic sources, which are estimated to comprise 90% of the global SOA burden, about half of which comes from isoprene. Compared to recent observations, it would appear there are additional pathways beyond those

  13. 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.

  14. 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...

  15. Formation of abnormal high pressure and its application in the study of oil-bearing property of lithologic hydrocarbon reservoirs in the Dongying Sag

    Institute of Scientific and Technical Information of China (English)

    ZHANG ShanWen; ZHANG LinYe; ZHANG ShouChun; LIU Qing; ZHU RiFang; BAO YouShu

    2009-01-01

    The mechanisms of abnormal high pressures are studied in this paper, and it is concluded that the undercompaction, hydrocarbon generation and stratum denudation are obviously effective to fluid pressure buildup. Because of the episodic difference, the hydrocarbon generation and stratum denu-dation are the main factors influencing oil-gas migration. On the basis of basin evolutionary analysis in the Dongying Sag, it is considered that the undercompaction mainly caused the abnormal pressure before the first denudation by the uplift in Late Paleogene, while hydrocarbon generation was the main factor of abnormal pressure after the denudation. The second denudation occurred in Late Neogene, which changed the pressure field and induced the fluid migration. The development of overpressures is the necessary condition to the formation of lithologic hydrocarbon reservoirs, which have positive correlations to overpressures. According to the fullness of the present reservoirs, the quantitative re-lations between oil-bearing property and driving forces of reservoir formation were determined, the latter were decided by dynamic source, reservoir capillary pressure, fluid pressure of surrounding rocks and the dynamic attenuation in different conducting systems.

  16. 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...

  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. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. Formation of halogenated disinfection by-products in cobalt-catalyzed peroxymonosulfate oxidation processes in the presence of halides.

    Science.gov (United States)

    Xie, Weiping; Dong, Wei; Kong, Deyang; Ji, Yuefei; Lu, Junhe; Yin, Xiaoming

    2016-07-01

    Sulfate radicals (SO4(-)) generated by activation of peroxymonosulfate (PMS) and persulfate (PS) are highly oxidative and applied to degrade various organic pollutants. This research was designed to investigate formation of halogenated by-products in Co(2+) activated PMS process in the presence of halides and natural organic matter (NOM). It was revealed that no halogenated by-products were detected in the presence of Cl(-) while 189 μg/L bromoform and 100.7 μg/L dibromoacetic acid (DBAA) were found after 120 h when 2 mg/L NOM, 0.1 mM Br(-), 1.0 mM PMS, and 5 μL Co(2+) were present initially. These products are known as disinfection by-products (DBPs) since they are formed in water disinfection processes. Formation of DBPs was even more significant in the absence of Co(2+). The data indicate that both PMS and SO4(-) can transform Br(-) to reactive bromine species which react with NOM to form halogenated by-products. Less DBP formation in Co(2+)-PMS systems was due to the further destruction of DBPs by SO4(-). More DBPs species including chlorinated ones were detected in the presence of both Cl(-) and Br(-). However, more brominated species produced than chlorinate ones generally. The total DBP yield decreased with the increase of Cl(-) content when total halides kept constant. This is one of the few studies that demonstrate the formation of halogenated DBPs in Co(2+)/PMS reaction systems, which should be taken into consideration in the application of SO4(-) based oxidation technologies. PMID:27093695

  4. 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...

  5. 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

  6. Fluids in the Palaeogene Formation of Gaoyou Sag in the Southern Part of North Jiangsu Basin, China: Evidence for Hydrocarbon Migration and Accumulation

    Science.gov (United States)

    LI, M.; Lou, Z.; Zhu, R.; Jin, A.

    2013-12-01

    Gaoyou Sag, lying in the middle of the Dongtai Depression in the North Jiangsu basin, China, has a well developed fault system and is characterised by structurally complicated oil and gas fields. Its oil-water relationship is very complicated. In the present study, we present the distribution of formation water chemistry, crude oil density, formation pressures and fluid potential in the Palaeogene formation of the Gaoyou Sag . The purpose of this article is to: (1) analyse the cause of hydrochemical diversity; (2) identify the flow pattern and evolution; and (3) understand the interplay between the flow of formation water and hydrocarbon migration and accumulation. The results showed that large variances in formation water chemistry occur in different oilfields of the Gaoyou Sag (Figure 1) due to dilution by meteoric water recharge, concentration by membrane filtration and complexity of geological structure. The low salinity (mean values from 8.53 g/L to 9.67 g/L) of the formation water and heavy crude oil density (up to 0.94g/cm3) in the Xuchuang oilfield indicate influence from meteoric water infiltration; the deep depression areas are mainly of connate origin. Geofluids in the Xuchuang, Zhenwu and Yang'an oilfields mainly flow vertically through the Zhenwu and Hanliu faults, while geofluids in the Shanian oilfield mainly migrate laterally through the reservoirs and are adjusted vertically along some cutting faults. Palaeo-hydrodynamic evolution had an affinity with the generation, migration, accumulation and preservation of hydrocarbons. In the depositional stages of the Dainan and Sanduo formations, formation water was expelled outward and upward from lacustrine mudstones of the deep depression into shallow sands of nearby oilfields, driven by compaction and overpressure. Hydrocarbon migrated with formation water and gathered in appropriate traps, forming primary reservoirs. During the Zhenwu and Sanduo movements, there were tectonic uplifts and the strata

  7. Formation, phase composition, texture and catalytic properties of Co-MgO-alumino-calcium catalysts in synthesis of hydrocarbons from CO and H/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Bruk, I.A.; Mal' tsev, V.V.; Iem, K.C.; Yakerson, V.I.; Golosman, Y.Z.; Mamayeva, I.A.; Kalacheva, N.B.; Danyushevskii, V.Y.; Nissenbaum, V.D.

    1981-01-01

    A study was made of the mechanism of formation of catalysts; a special feature of this mechanism is the interaction of components (calcium aluminates and basic carbonates of cobalt and magnesium); the carrier with a developed surface and the active component distributed on this surface are formed during this process. Catalysts show maximum selectivity in synthesis of liquid hydrocarbons from CO and H/sub 2/ with a degree of reduction of the metal of 65-84% and a dispersion (according to chemisorption of CO) of 6 x 10/sup -3/ - 10 x 10/sup -3/. Maximum yield of liquid hydrocarbons (114.1 g/nm/sup 3/) was obtained in the pressure of a system of 33Co-3MgO-64 talum treated with hydrogen at 550/sup 0/C.

  8. An arginine-aspartate network in the active site of bacterial TruB is critical for catalyzing pseudouridine formation.

    Science.gov (United States)

    Friedt, Jenna; Leavens, Fern M V; Mercier, Evan; Wieden, Hans-Joachim; Kothe, Ute

    2014-04-01

    Pseudouridine synthases introduce the most common RNA modification and likely use the same catalytic mechanism. Besides a catalytic aspartate residue, the contributions of other residues for catalysis of pseudouridine formation are poorly understood. Here, we have tested the role of a conserved basic residue in the active site for catalysis using the bacterial pseudouridine synthase TruB targeting U55 in tRNAs. Substitution of arginine 181 with lysine results in a 2500-fold reduction of TruB's catalytic rate without affecting tRNA binding. Furthermore, we analyzed the function of a second-shell aspartate residue (D90) that is conserved in all TruB enzymes and interacts with C56 of tRNA. Site-directed mutagenesis, biochemical and kinetic studies reveal that this residue is not critical for substrate binding but influences catalysis significantly as replacement of D90 with glutamate or asparagine reduces the catalytic rate 30- and 50-fold, respectively. In agreement with molecular dynamics simulations of TruB wild type and TruB D90N, we propose an electrostatic network composed of the catalytic aspartate (D48), R181 and D90 that is important for catalysis by fine-tuning the D48-R181 interaction. Conserved, negatively charged residues similar to D90 are found in a number of pseudouridine synthases, suggesting that this might be a general mechanism.

  9. Cofactor requirements and reconstitution of microcin B17 synthetase: a multienzyme complex that catalyzes the formation of oxazoles and thiazoles in the antibiotic microcin B17.

    Science.gov (United States)

    Milne, J C; Roy, R S; Eliot, A C; Kelleher, N L; Wokhlu, A; Nickels, B; Walsh, C T

    1999-04-13

    In the maturation of the Escherichia coli antibiotic Microcin B17 (MccB17), the McbA prepro-antibiotic is modified post-translationally by the multimeric microcin synthetase complex (composed of the McbB, -C, and -D proteins), which cyclizes four cysteines and four serines to thiazoles and oxazoles, respectively. Herein, we report the purification of individual subunits of MccB17 synthetase as fusions to maltose binding protein (MBP), and the in vitro reconstitution of heterocyclization activity. Preliminary characterization of each subunit reveals McbB to be a zinc-containing protein that may catalyze the initial cyclodehydration step, and McbC to contain flavin, consistent with an anticipated role for a dehydrogenase. We have previously demonstrated that McbD is a regulated ATPase/GTPase that may function as a conformational switch. Photolabeling experiments with the McbA propeptide now identify McbD as the initial site of substrate recognition. Heterocyclization activity was reconstituted only by combining all three subunits, demonstrating that each protein is required for heterocycle formation. Titration assays indicate that the subunits bind to each other with at least micromolar affinities, although McbD affords activity only after the MBP tag is proteolytically removed. Subunit competition assays with an McbDD147A mutant, which yields a catalytically deficient synthetase in vivo, show it to be defective in complex formation, whereas the McbBC181A/C184A double mutant, which is also inactive, competitively inhibits reconstitution by native McbB. Addition of the HtpG chaperone (originally shown to copurify with MccB17 synthetase), does not stimulate synthetase reconstitution or heterocyclization activity in vitro. A model for synthetase activity is proposed.

  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. An apparatus for vapor conversion of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Tabata, K.; Matsumoto, I.

    1983-03-23

    The installation for vapor conversion of hydrocarbons (Uv) with the formation of a mixture of H2 and C02 is a catalyst chamber (KK) filled with longitudinally disposed thin pipes (with thin walls) or with pipe units made of dolomite, MgO or potassium aluminate. These pipes have a multilayered coating (Pk) on their internal and external surfaces (Pv), which contain catalytically active components. Such pipes or pipe units form a honeycombed structure with through longitudinal channels. The catalyst chamber itself is made of a ceramic material and has a heating winding outside for heating the catalyst. To save fuel and to increase the efficiency (KPD) of the heating device, the catalyst chamber is in turn enclosed by two additional shells filled with heat conducting packings which are easily penetrated by the gases being processed. The hydrocarbon vapors or gaseous fuel from the natural gas or methane and the steam are fed through the above cited heat exchange layers with packings into the facial part of the catalytic chamber, in which the conversion of the hydrocarbons occurs with the production of H2 and C02. From the catalyzer layer the mixture of gases and steam goes through a refrigerator into a trap for the steam excess and when it is necessary, into a C02 absorber and then, pure H2 is discharged from the latter. Such a catalytic installation is convenient to use for producing pure H2 from natural gas, methane, propane or kerosene.

  13. 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.

  14. Effect of acid-catalyzed formation rates of benzimidazole-linked polymers on porosity and selective CO2 capture from gas mixtures.

    Science.gov (United States)

    Altarawneh, Suha; İslamoğlu, Timur; Sekizkardes, Ali Kemal; El-Kaderi, Hani M

    2015-04-01

    Benzimidazole-linked polymers (BILPs) are emerging candidates for gas storage and separation applications; however, their current synthetic methods offer limited control over textural properties which are vital for their multifaceted use. In this study, we investigate the impact of acid-catalyzed formation rates of the imidazole units on the porosity levels of BILPs and subsequent effects on CO2 and CH4 binding affinities and selective uptake of CO2 over CH4 and N2. Treatment of 3,3'-Diaminobenzidine tetrahydrochloride hydrate with 1,2,4,5-tetrakis(4-formylphenyl)benzene and 1,3,5-(4-formylphenyl)-benzene in anhydrous DMF afforded porous BILP-15 (448 m(2) g(-1)) and BILP-16 (435 m(2) g(-1)), respectively. Alternatively, the same polymers were prepared from the neutral 3,3'-Diaminobenzidine and catalytic amounts of aqueous HCl. The resulting polymers denoted BILP-15(AC) and BILP-16(AC) exhibited optimal surface areas; 862 m(2) g(-1) and 643 m(2) g(-1), respectively, only when 2 equiv of HCl (0.22 M) was used. In contrast, the CO2 binding affinity (Qst) dropped from 33.0 to 28.9 kJ mol(-1) for BILP-15 and from 32.0 to 31.6 kJ mol(-1) for BILP-16. According to initial slope calculations at 273 K/298 K, a notable change in CO2/N2 selectivity was observed for BILP-15(AC) (61/50) compared to BILP-15 (83/63). Similarly, ideal adsorbed solution theory (IAST) calculations also show the higher specific surface area of BILP-15(AC) and BILP-16(AC) compromises their CO2/N2 selectivity.

  15. Distribution and geological significance of 17α(H)-diahopanes from different hydrocarbon source rocks of Yanchang Formation in Ordos Basin

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Based on GC-MS testing data of many saturated hydrocarbon samples, 17α(H)-C30 diahopanes (C30*) are extensively distributed in the lacustrine hydrocarbon source rocks of the Yanchang Formation in Ordos Basin, but show remarkable differences in relative abundance among various source rocks. Generally, Chang 7 high-quality source rock (oil shale) developed in deep lake anoxic environment shows lower C30* content, whereas Chang 6-9 dark mudstone developed in shallow to semi-deep lake, sub-oxidizing environment shows relatively high to high C30* value. Particularly, Chang 7 and Chang 9 black mudstones in Zhidan region in the northeast of the lake basin show extremely high C30* value. A comparative analysis was made based on lithology, organic types and various geochemical parameters indicative of redox environment, and the results indicate that environmental factors such as redox settings and lithology are key factors that control the C30* relative abundance, while organic types and maturity may be minor factors. High to extremely high C30* values are indicative of sub-oxidizing environment of fresh-brackish water and shallow to semi-deep lake. Therefore, research on C30* relative content and distribution in lacustrine hydrocarbon source rocks in the Yanchang Formation, especially on the difference in C30* between Chang 7 high-quality source rocks (oil shale) and Chang 6-91 source rocks (dark mudstone), will provide an important approach for classification of Mesozoic lacustrine crudes and detailed oil-source correlation in the basin.

  16. Distribution and geological significance of 17α(H)-diahopanes from different hydrocarbon source rocks of Yanchang Formation in Ordos Basin

    Institute of Scientific and Technical Information of China (English)

    ZHANG WenZheng; YANG Hua; HOU LiHui; LIU Fei

    2009-01-01

    Based on GC-MS testing data of many saturated hydrocarbon samples, 17α(H)-30 diahopanes (C30*) are extensively distributed in the lacustrine hydrocarbon source rocks of the Yanchang Formation in Ordos Basin, but show remarkable differences in relative abundance among various source rocks. Generally, Chang 7 high-quality source rock (oil shale) developed in deep lake anoxic environment shows lower C30* content, whereas Chang 6-9 dark mudstone developed in shallow to semi-deep lake, sub-oxidiz- ing environment shows relatively high to high C30* value. Particularly, Chang 7 and Chang 9 black mudstones in Zhidan region in the northeast of the lake basin show extremely high C30* value. A com- parative analysis was made based on lithology, organic types and various geochemical parameters indicative of redox environment, and the results indicate that environmental factors such as redox set- tings and lithology are key factors that control the C30* relative abundance, while organic types and maturity may be minor factors. High to extremely high C30* values are indicative of sub-oxidizing envi- ronment of fresh-brackish water and shallow to semi-deep lake. Therefore, research on C30* relative content and distribution in lacustrine hydrocarbon source rocks in the Yanchang Formation, especially on the difference in C30* between Chang 7 high-quality source rocks (oil shale) and Chang 6-91 source rocks (dark mudstone), will provide an important approach for classification of Mesozoic lacustrine crudes and detailed oil-source correlation in the basin.

  17. 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

  18. 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

  19. 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

  20. 深部热流体对油气成藏的影响%Influences of Deeply Sourced Thermal Fluid on the Formation of Hydrocarbon Reservoirs

    Institute of Scientific and Technical Information of China (English)

    高波; 陶明信; 王万春

    2001-01-01

    Deeply sourced thermal fluid is a kind of supercritical fluidcomposed of several constituents. Rising upward, it can transmit energy and material, and regulate and redistribute them in the inner Earth. For the formation of oil and gas, hypogene hydrothermal fluid can increase the paleotemperature of depositional basin, accelerate the evolution history of source rocks and enlarge the volume of effective source rocks. It can also extract and enrich dispersive organic matter in sediments because of its higher dissolving and diffusing capacity, and obviously contribute hydrogen to hydrocarbon generation. So the deeply sourced thermal fluid provides part of material resources for hydrocarbon generation. In addition, the reaction between thermal fluid and surrounding rocks can improve their porosity and permeability. This is favorable for the migration and accumulation of hydrocarbons. Moreover, that the higher pressure and water content of thermal fluid can significantly retard the thermal destruction of hydrocarbon is advantageous to the preservation of oil and gas.%深部热流体是一种由多元组分构成的超临界流体,其上升活动可使地球内部的物质与能量发生调整或再分配。对油气而言,深部热流体携带的高热能可使沉积盆地的古地温升高,加快烃源岩的热演化进程,增加有效烃源岩的体积,促进烃类的生成;在上升过程中,因其具很强的溶解和扩散能力,故可萃取、富集沉积物中的分散有机质,同时又对生烃产生显著的加氢作用,从而为油气的形成补充物源。此外,热流体与围岩储层发生化学反应,可改善储层的孔渗条件,有利于油气的聚集成藏,而且因其具有较高的压力和含水量,可抑制烃类的热裂解而有利于油气的保存。

  1. Crossed beam investigation of elementary reactions relevant to the formation of polycyclic aromatic hydrocarbon (PAH)-like molecules in extraterrestrial environments

    Science.gov (United States)

    Kaiser, R. I.; Asvany, O.; Lee, Y. T.

    2000-04-01

    The reactions of ground state carbon atoms, C( 3P j), with benzene, C 6H 6, and phenyl radicals, C 6H 5, with methylacetylene, CH 3CCH, were investigated in crossed beam experiments at collision energies of 21.8 and 140 kJ mol -1 to investigate elementary reactions relevant to the formation and chemistry of polycyclic aromatic hydrocarbons (PAHs) in extraterrestrial environments. The C( 3P j) reaction proceeds via complex formation and gives a cyclic, seven-membered C 7H 5 doublet radical plus atomic hydrogen. This pathway has neither an entrance nor exit barrier, and is exothermic. Together with the experimental verification of the carbon versus hydrogen exchange under single collision conditions, the findings have an important impact on the chemistry of aromatic molecules in interstellar clouds and outflow of carbon stars. Even in the coldest molecular clouds ( T=10 K), the benzene molecule can be destroyed upon reaction with carbon atoms, whereas they are resistant toward an attack of oxygen and nitrogen atoms. Since the aromatic benzene unit is ubiquitous in extraterrestrial, PAH-like material, our results suggest that PAHs might react with carbon atoms as well. On the other side, the reaction of C 6H 5 radicals with methylacetylene to form phenylmethylacetylene is direct. Since an entrance barrier inhibits the reaction in cold molecular clouds and in the atmospheres of hydrocarbon rich planets like Jupiter and Saturn and satellites such as Titan, this reaction is expected to play a role in PAH synthesis only in high temperature interstellar environments, such as circumstellar outflows of carbon stars.

  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. 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

  4. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu

    2016-01-01

    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  5. 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

  6. 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...

  7. Inhibition of the formation of benzo[a]pyrene adducts to DNA in A549 lung cells exposed to mixtures of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Genies, Camille; Jullien, Amandine; Lefebvre, Emmanuel; Revol, Morgane; Maitre, Anne; Douki, Thierry

    2016-09-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants, which exhibit carcinogenic properties especially in lungs. In the present work, we studied the effect of mixtures of 12 PAHs on the A549 alveolar cells. We first assess the ability of each PAH at inducing gene expression of phase I metabolization enzymes and at generating DNA adducts. A good correlation was found between these two endpoints. We then exposed cells to either binary mixtures of the highly genotoxic benzo[a]pyrene (B[a]P) with each PAH or complex mixtures of all studied PAHs mimicking by real emissions including combustion of wood, cigarette smoke, and atmospheres of garage, silicon factory and urban environments. Compared to pure B[a]P, both types of mixtures led to reduced CYP450 activity measured by the EROD test. A similar trend was observed for the formation of DNA adducts. Surprisingly, the complex mixtures were more potent than B[a]P used at the same concentration for the induction of genes coding for CYP. Our results stress the lack of additivity of the genotoxic properties of PAH in mixtures. Interestingly, an opposite synergy in the formation of B[a]P adducts were observed previously in hepatocytes. Our data also show that measurement of the metabolic activity rather than quantification of gene expression reflects the actual bioactivation of PAHs into DNA damaging species. PMID:27196671

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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...

  14. 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

  15. 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

    Science.gov (United States)

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

    2015-03-01

    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 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 the 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 NMHC that are abundant in condensate, in particular toluene and m+p-xylene. Emissions from water treatment have an influence upon peak O3 mixing ratios at downwind measurement sites.

  16. 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.

  17. 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.

  18. 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

  19. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  20. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    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 ...

  1. 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.

  2. THERMOCHEMISTRY OF HYDROCARBON RADICALS

    Energy Technology Data Exchange (ETDEWEB)

    Kent M. Ervin, Principal Investigator

    2004-08-17

    Gas phase negative ion chemistry methods are employed to determine enthalpies of formation of hydrocarbon radicals that are important in combustion processes and to investigate the dynamics of ion-molecule reactions. Using guided ion beam tandem mass spectrometry, we measure collisional threshold energies of endoergic proton transfer and hydrogen atom transfer reactions of hydrocarbon molecules with negative reagent ions. The measured reaction threshold energies for proton transfer yield the relative gas phase acidities. In an alternative methodology, competitive collision-induced dissociation of proton-bound ion-molecule complexes provides accurate gas phase acidities relative to a reference acid. Combined with the electron affinity of the R {center_dot} radical, the gas phase acidity yields the RH bond dissociation energy of the corresponding neutral molecule, or equivalently the enthalpy of formation of the R{center_dot} organic radical, using equation: D(R-H) = {Delta}{sub acid}H(RH) + EA(R) - IE(H). The threshold energy for hydrogen abstraction from a hydrocarbon molecule yields its hydrogen atom affinity relative to the reagent anion, providing the RH bond dissociation energy directly. Electronic structure calculations are used to evaluate the possibility of potential energy barriers or dynamical constrictions along the reaction path, and as input for RRKM and phase space theory calculations. In newer experiments, we have measured the product velocity distributions to obtain additional information on the energetics and dynamics of the reactions.

  3. 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

  4. An x-ray photoemission electron microscopy study of the formation of Ti-Al phases in 4 mol% TiCl3 catalyzed NaAlH4 during high energy ball milling

    Science.gov (United States)

    Dobbins, Tabbetha; Abrecht, Mike; Uprety, Youaraj; Moore, Kristan

    2009-05-01

    This study reports reaction pathways to form TiAlx metallic complexes during the high energy ball milling of 4 mol% TiCl3 with NaAlH4 powders determined using local structure analysis of Tix+ and Alx+ species. Using x-ray photoemission electron microscopy (XPEEM) and x-ray diffraction (XRD), the oxidation state of Alx+ and Tix+ and the crystalline compounds existing in equilibrium with NaAlH4 were tracked for samples milled for times of 0 (i.e. mixing), 5, and 25 min. XPEEM analysis of the Al K edge after 5 min of milling reveals that Al remains in the 3+ oxidation state (i.e. in NaAlH4) around Ti0-rich regions of the sample. After 25 min of high energy milling, Ti0 has reacted with Al3+ (in nearby NaAlH4) to form TiAlx complexes. This study reports the pathway for TiAlx complex formation during milling of 4 mol% TiCl3 catalyzed NaAlH4 to be as follows: (1) Ti3+ reduces to Ti0 (with Al3+ near Ti0 regions) and (2) Ti0 reacts with Al3+ in NaAlH4 to form TiAlx complexes.

  5. 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

  6. 鄂尔多斯盆地富县—正宁地区延长组油气成藏期次%Classification of hydrocarbon accumulation phases of the Yanchang Formation in the Fuxian-Zhengning area, Ordos Basin

    Institute of Scientific and Technical Information of China (English)

    梁宇; 任战利; 史政; 赵筱燕; 于强; 吴晓青

    2011-01-01

    鄂尔多斯盆地富县—正宁地区延长组砂岩储层主要成岩作用有压实作用、胶结作用、溶蚀作用和裂隙作用,成岩自生矿物以绿泥石、自生石英和方解石为主.根据油气包裹体寄主成岩矿物的形成时间序列,识别出两期油气包裹体:第1期油气包裹体主要分布在石英、长石粒内愈合的、未切穿次生加大边的微裂隙及石英次生加大边内侧;第2期油气包裹体分布在晚期微裂隙和晚期亮晶方解石胶结物中.油气包裹体均一温度分布呈双峰型:早期峰值温度为110~120℃;晚期峰值温度为140~150℃.对油气包裹体均一温度、盐度、密度分析表明,研究区延长组油气为“一期两幕”成藏,且具有“边致密,边成藏”的特点.结合研究区延长组热演化史及储层伊利石K-Ar同位素定年结果研究表明,研究区主要油气成藏期为早白垩世(距今95~120Ma).%The main diagenesis of the Yanchang Formation sandstone reservoirs in the Fuxian-Zhengning area, Ordos Basin, includes compaction, cementation, corrosion and fracturation, and diagenetic authigenic minerals in these reservoirs are dominated by chlorite, authigenetic quartz and calcite. Two phases of hydrocarbon inclusions have been identified according to the time sequence of the formation of host diagenetic minerals, the earlier one composed of mostly brine inclusions that contain gaseous or liquid hydrocarbons either occurs along healed microfractures wrapped up by secondary growth edges of quartz or feldspar, or is trapped at the bottom of secondary growth edges of quartz or feldspar, while the later one mostly consisting of gas-liquid or liquid hydrocarbon inclusions occurs along the late-formed microfractures or in sparry calcite cements. Homogenization temperatures measured from brine inclusions associated with hydrocarbon ones show a bimodal distribution in the ranges with 110~120'C and 140~150'C as peak temperatures

  7. 鄂尔多斯盆地延长组下组合油气来源及成藏模式%Hydrocarbon origin and reservoir forming model of the Lower Yanchang Formation, Ordos Basin

    Institute of Scientific and Technical Information of China (English)

    李相博; 刘显阳; 周世新; 刘化清; 陈启林; 王菁; 廖建波; 黄军平

    2012-01-01

    通过生物标志化合物对比、流体包裹体分析及盆地模拟研究,对鄂尔多斯盆地延长组长9与长10油层组的油源、成藏期次及成藏模式进行了探讨.陇东与姬塬地区长9油层组的原油分为2种类型,第Ⅰ类来源于长7烃源岩,第Ⅱ类来源于长9烃源岩;陕北地区长10油层组的原油主要来源于长9烃源岩.陇东与姬塬地区长9油藏均发生过2期油气充注,但前者在第1期(中侏罗统直罗组沉积期)就达到了油气充注的高峰期,而后者在第2期(下白垩统志丹组沉积期)才达到油气充注高峰期;陕北长10油层组也存在2期成藏,但2期油气呈连续充注,大致从中侏罗统直罗组沉积早期一直持续到下白垩统志丹组沉积中后期.长9与长10油藏有“上生下储”、“侧生旁储”及“自生自储”3种成藏模式.图10参22%According to the comparison of biomarkers in source rocks and crude oil, fluid inclusion analysis, and basin modeling, this paper discusses the oil source, hydrocarbon accumulation period and reservoir forming model of the Chang 9 and Chang 10 oil-bearing formations, Yanchang Formation, Ordos Basin. The crude oil of Chang 9 in the Longdong and Jiyuan areas can be divided into two types, type I crude oil originated from the source rocks within Chang 7, while type II crude oil came from the source rocks within Chang 9. The crude oil of Chang 10 in Northern Shaanxi originated mainly from the source rocks of Chang 9. The Chang 9 oil reservoirs in both the Longdong and Jiyuan areas experienced two periods of hydrocarbon injection. The former reached the peak period of hydrocarbon injection in the first period (the depositional period of Middle Jurassic Zhiluo Formation), while the latter in the second period (the depositional period of Lower Cretaceous Zhidan Formation). There are two periods of continuous hydrocarbon injection in Chang 10 of Northern Shaanxi, generally from the early depositional period of

  8. 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)

  9. An x-ray photoemission electron microscopy study of the formation of Ti-Al phases in 4 mol% TiCl{sub 3} catalyzed NaAlH{sub 4} during high energy ball milling

    Energy Technology Data Exchange (ETDEWEB)

    Dobbins, Tabbetha; Uprety, Youaraj [Institute for Micromanufacturing, Louisiana Tech University, 911 Hergot Avenue, Ruston, LA 71272 (United States); Abrecht, Mike [Synchrotron Radiation Center, University of Wisconsin at Madison, 3731 Schneider Drive, Madison, WI 53789 (United States); Moore, Kristan [Department of Physics, Grambling State University, Grambling, LA 71245 (United States)

    2009-05-20

    This study reports reaction pathways to form TiAl{sub x} metallic complexes during the high energy ball milling of 4 mol% TiCl{sub 3} with NaAlH{sub 4} powders determined using local structure analysis of Ti{sup x+} and Al{sup x+} species. Using x-ray photoemission electron microscopy (XPEEM) and x-ray diffraction (XRD), the oxidation state of Al{sup x+} and Ti{sup x+} and the crystalline compounds existing in equilibrium with NaAlH{sub 4} were tracked for samples milled for times of 0 (i.e. mixing), 5, and 25 min. XPEEM analysis of the Al K edge after 5 min of milling reveals that Al remains in the 3+ oxidation state (i.e. in NaAlH{sub 4}) around Ti{sup 0}-rich regions of the sample. After 25 min of high energy milling, Ti{sup 0} has reacted with Al{sup 3+} (in nearby NaAlH{sub 4}) to form TiAl{sub x} complexes. This study reports the pathway for TiAl{sub x} complex formation during milling of 4 mol% TiCl{sub 3} catalyzed NaAlH{sub 4} to be as follows: (1) Ti{sup 3+} reduces to Ti{sup 0} (with Al{sup 3+} near Ti{sup 0} regions) and (2) Ti{sup 0} reacts with Al{sup 3+} in NaAlH{sub 4} to form TiAl{sub x} complexes.

  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. 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

  12. 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.).

  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. Biological enhancement of hydrocarbon extraction

    Science.gov (United States)

    Brigmon, Robin L.; Berry, Christopher J.

    2009-01-06

    A method of microbial enhanced oil recovery for recovering oil from an oil-bearing rock formation is provided. The methodology uses a consortium of bacteria including a mixture of surfactant producing bacteria and non-surfactant enzyme producing bacteria which may release hydrocarbons from bitumen containing sands. The described bioprocess can work with existing petroleum recovery protocols. The consortium microorganisms are also useful for treatment of above oil sands, ground waste tailings, subsurface oil recovery, and similar materials to enhance remediation and/or recovery of additional hydrocarbons from the materials.

  15. 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...

  16. 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)

  17. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. V. Chemical dynamics of n-C4H3 formation from reaction of C(3Pj) with allene, H2CCCH2(X 1A1)

    Science.gov (United States)

    Kaiser, R. I.; Mebel, A. M.; Chang, A. H. H.; Lin, S. H.; Lee, Y. T.

    1999-06-01

    The crossed molecular beams technique was employed to investigate the reaction between ground state carbon atoms, C(3Pj), and allene, H2CCCH2(X 1A1), at two averaged collision energies of 19.6 and 38.8 kJ mol-1. Product angular distributions and time-of-flight spectra of C4H3 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The maximum translational energy release and the angular distributions combined with ab initio and RRKM calculations are consistent with the formation of the n-C4H3 radical in its electronic ground state. The channel to the i-C4H3 isomer contributes less than 1.5%. Reaction dynamics inferred from the experimental data indicate that the carbon atom attacks the π-orbitals of the allenic carbon-carbon double bond barrierless via a loose, reactant-like transition state located at the centrifugal barrier. The initially formed cyclopropylidene derivative rotates in a plane almost perpendicular to the total angular momentum vector around its C-axis and undergoes ring opening to triplet butatriene. At higher collision energy, the butatriene complex decomposes within 0.6 ps via hydrogen emission to form the n-C4H3 isomer and atomic hydrogen through an exit transition state located 9.2 kJ mol-1 above the products. The explicit identification of the n-C4H3 radical under single collision represents a further example of a carbon-hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a barrierless route to synthesize extremely reactive hydrocarbon radicals in combustion processes, interstellar chemistry, and hydrocarbon-rich atmospheres of Jupiter, Saturn, Titan, as well as Triton.

  18. 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.

  19. 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.

  20. 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.

  1. 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 water. The results indicate that HNO3 was only weakly dissociated in the 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.

  2. 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

  3. Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

    Science.gov (United States)

    Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

    2014-05-16

    A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

  4. 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

  5. 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.

  6. Electrochemical reduction characteristics and the mechanism of chlorinated hydrocarbons at the copper electrode

    Institute of Scientific and Technical Information of China (English)

    XU Wenying; GAO Tingyao; ZHOU Rongfeng; MA Lumin

    2007-01-01

    The electrochemical reduction characteristies of chlorinated hyrdrocarbons were investigated by cyclic voltammetry technique.The reduction mechanism and activity of the chlorinated hydrocarbons at the copper electrode were explored.The relationship between the structure of chlorinated hydrocarbons and their reductive activity were discussed.The experimental results showed that chlorinated alkanes and a portion of chlorinated aromatic hydrocarbons could be reduced directly at the copper electrode.However,chlorinated aromatic hydrocarbons were not easy to reduce at the copper electrode.The results provided a theoretical basis for the catalyzed iron inner electrolysis method.

  7. 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

  8. 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.

  9. 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.)

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.

    Science.gov (United States)

    Hoyt, Jordan M; Schmidt, Valerie A; Tondreau, Aaron M; Chirik, Paul J

    2015-08-28

    Cycloadditions, such as the [4+2] Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous [2+2] alkene cycloaddition to synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular [2+2] cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal-catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks.

  20. 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.

  1. Palladium-Catalyzed Modification of Unprotected Nucleosides, Nucleotides, and Oligonucleotides

    Directory of Open Access Journals (Sweden)

    Kevin H. Shaughnessy

    2015-05-01

    Full Text Available Synthetic modification of nucleoside structures provides access to molecules of interest as pharmaceuticals, biochemical probes, and models to study diseases. Covalent modification of the purine and pyrimidine bases is an important strategy for the synthesis of these adducts. Palladium-catalyzed cross-coupling is a powerful method to attach groups to the base heterocycles through the formation of new carbon-carbon and carbon-heteroatom bonds. In this review, approaches to palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides are reviewed. Polar reaction media, such as water or polar aprotic solvents, allow reactions to be performed directly on the hydrophilic nucleosides and nucleotides without the need to use protecting groups. Homogeneous aqueous-phase coupling reactions catalyzed by palladium complexes of water-soluble ligands provide a general approach to the synthesis of modified nucleosides, nucleotides, and oligonucleotides.

  2. 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.

  3. 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

  4. 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

  5. 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.

  6. Utilization of biomass: Conversion of model compounds to hydrocarbons over zeolite H-ZSM-5

    DEFF Research Database (Denmark)

    Mentzel, Uffe Vie; Holm, Martin Spangsberg

    2011-01-01

    Zeolite catalyzed deoxygenation of small oxygenates present in bio-oil or selected as model compounds was performed under Methanol-to-Hydrocarbons (MTH) like reaction conditions using H-ZSM-5 as the catalyst. Co-feeding of the oxygenates with methanol generally decreases catalyst lifetime due....../ester functionalities favor oxygen removal through decarbonylation over dehydration which preserves hydrogen in the hydrocarbon product mixture. By employing 13C labeled substrates we confirmed the incorporation of carbon into the hydrocarbon products as well as a pronounced preference of the additive carbon towards...

  7. 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.

  8. 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

  9. Hydrocarbon potential of source rocks in the Middle Triassic Leikoupo Formation in the Western Sichuan Depression%四川盆地西部中三叠统雷口坡组烃源岩生烃潜力分析

    Institute of Scientific and Technical Information of China (English)

    杨克明

    2016-01-01

    中三叠统雷口坡组是近年来四川盆地海相天然气勘探的重要层系之一.通过对川西地区雷口坡组钻井样品的有机地球化学分析,结合地震解释资料及沉积相资料,推测雷口坡组烃源岩主要分布在大邑—温江—彭州—广汉及孝泉地区,烃源岩厚度达250~350 m,有机碳含量为0.4%~0.6%.川西雷口坡组烃源岩形成于生物生产力较高、水动力较弱、海水循环受限、盐度较高、沉积物—水界面附近缺氧和沉积速率较低的沉积环境,有利于烃源岩有机质的保存.川西地区雷口坡组烃源岩有机、无机地球化学和有机岩石学综合分析表明,该烃源岩虽然有机质丰度较低,但类型较好;烃源岩有机质显微组分中常见固体沥青和超微组分,有机质类型指数TI为12.5%~98.03%,主要为Ⅱ1-Ⅱ2型烃源岩,有机质主要来源于水生浮游生物,具有较好的生烃潜力.%The Middle Triassic Leikoupo Formation in the Western Sichuan Depression is an important marine target for natural gas exploration in the Sichuan Basin in recent years. Geochemical analyses were made with rock samples from the Leikoupo Formation. Seismic interpretation and sedimentary data were studied. Source rocks in the Leikoupo Formation mainly distribute in Dayi, Wenjiang, Pengzhou, Guanghan and Xiaoquan. They are about 250-350 m thick, and have a TOC content of 0.4%-0.6%. The source rocks were deposited in a sedimen?tary environment with high biological productivity, quiescent depositional setting, restricted seawater circulation, high salinity, anoxic bottom water and low deposition rate, all favorable for the preservation of organic matter. The comprehensive analyses of organic geochemistry, inorganic geochemistry and organic petrology indicated that, the source rocks in the Leikoupo Formation displayed a low abundance of organic matter with good organic type. Solid bitumen and ultramicro macerals were observed on photomicrographs

  10. 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).

  11. 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

  12. 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.

  13. Effects of hydrocarbon physical properties on caprock’s capillary sealing ability

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A new mechanics formula of caprock’s capillary sealing ability has been established in this paper, in which the boundary layer resistance was considered and characterized by starting pressure gradient. The formula shows that capillary sealing ability of caprock is determined not only by the capillary force of rock and the buoyancy of hydrocarbon column, but also by the starting pressure gradient of hydrocarbons and the thickness of caprock. The buoyancy of hydrocarbon column, the starting pressure gradient of hydrocarbon, and the capillary force of caprock are affected by hydrocarbon density, hydrocarbon viscosity, and hydrocarbon-water interface tension respectively. Based on hydrocarbon property data of reservoirs of Jiyang Depression and equations from literature, the effects of hydrocarbon density, hydrocarbon viscosity, and hydrocarbon-water interface tension on the sealing ability of caprock are analyzed. Under formational conditions, the sealing ability of oil caprock can vary up to dozens times because of the variations of the oil density, oil viscosity, and oil-water interface tension. Thus, the physical characters of hydrocarbon should be considered when evaluating the capillary sealing ability of caprocks. Study of the effects of physical characters on sealing ability of caprock can provide guidance to exploring special physical property hydrocarbon resources, such as viscous oils, and hydrocarbon resources in special pressure-temperature environments.

  14. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vinegar, Harold J. (Bellaire, TX); Stanecki, John (Blanco, TX)

    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.

  16. 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 <8 × 10(-4), at least a factor of 10(4) less than that for HNO3 in water. The results indicate that HNO3 was only weakly dissociated in the 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

  17. 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.

  18. Gold-Catalyzed Synthesis of Heterocycles

    Science.gov (United States)

    Arcadi, Antonio

    2014-04-01

    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  19. 高邮凹陷北斜坡戴南组原油运移特征分析%Hydrocarbon migration characteristics of Dainan Formation in Northern Slope of Gaoyou Sag

    Institute of Scientific and Technical Information of China (English)

    李兴丽; 张秀文; 王骏; 刘平兰; 宋宁

    2011-01-01

    In Dainan Formation of the research area, the display of oil and gas is very active and the accumulation condition is good. Two oil families ,that is oil from E2f4 and E1f2 respectively, have been recognized according to the oil geochemical characteristics of Hua 24, Hua3, Hual3, Hua6 and Sha49. Migration directions of hydrocarbon are discussed by geochemical parameters such as physical and chemical properties, biomarker compound, and nitrogen compounds. Research results show that oil of E1f4 mainly came from the dark mudstone of E1f4;the oil sources of E1f2 is mainly came from the nearby mature source rock of E1f2, and accumulated through long distance vertical migration.%研究区戴南组油气显示活跃,成藏条件有利。通过对花24块、花3块、花13块、花6块以及沙49块戴南组原油地球化学特征分析,确定了研究区戴南组原油的来源问题,并据不同油源将研究区内戴南组原油分为两种类型,即阜四段原油和阜二段原油。综合研究了原油的物理、化学性质以及生物标志物、含氮化合物等特征,详细分析了原油的运移方向。研究结果表明戴南组原油中阜四段油源主要来自深凹带刘五舍次凹成熟的阜四段烃源岩,阜二段油源主要来自附近成熟的阜二段烃源岩生油.经长距离垂向运移成藏。

  20. 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.

  1. 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

  2. Asymmetric Aldol Reaction Catalyzed by Modularly Designed Organocatalysts

    Institute of Scientific and Technical Information of China (English)

    Sinha, Debarshi; Mandal, Tanmay; Gogoi, Sanjib; Goldman, Joshua J.; 赵从贵

    2012-01-01

    The self-assembly of the precatalyst modules, which are amino acids and cinchona alkaloid derivatives, leads to the direct formation of the desired organocatalysts without any synthesis. These modularly designed organocatalysts (MDOs) may be used for catalyzed asymmetric aldol reaction the corresponding aldol products may be obtained in mediocre diastereoselectivities (up to 79 : 21 dr). Depending on structure of the aldehyde substrates, to excellent ee values (up to 92% ee) with moderate

  3. 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.

  4. 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

  5. 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.

  6. Hydrocarbon activation under sulfate-reducing and methanogenic conditions proceeds by different mechanisms.

    Science.gov (United States)

    Head, Ian; Gray, Neil; Aitken, Caroline; Sherry, Angela; Jones, Martin; Larter, Stephen

    2010-05-01

    Microbial degradation of alkanes typically involves their conversion to fatty acids which are then catabolised by beta-oxidation. The critical step in this process is activation of the hydrocarbon. Under oxic conditions this is catalyzed by monooxygenase enzymes with the formation of long chain alcohols. In the absence of oxygen alternative alkane activation mechanisms have been observed or proposed. Fumarate addition to alkanes to form alkyl succinates is considered a central process in anaerobic hydrocarbon degradation. Comparative studies of crude oil degradation under sulphate-reducing and methanogenic conditions revealed distinctive patterns of compound class removal and metabolite formation. Alkyl succinates derived from C7 to C26 n-alkanes and branched chain alkanes were found in abundance in sulfate-reducing systems but these were not detected during methanogenic crude oil degradation. Only one other mechanism of alkane activation has been elucidated to date. This involves addition of carbon derived from bicarbonate/CO2 to C-3 of an alkane chain to form a 2-ethylalkane with subsequent removal of the ethyl group leading to the formation of a fatty acid 1 carbon shorter than the original alkane. 2-ethylalkanes have never been detected as metabolites of anaerobic alkane degradation and were not detected in crude oil-degrading methanogenic systems. Due to the range of alkanes present in crude oil it was not possible to infer the generation of C-odd acids from C-even alkanes which is characteristic of the C-3 carboxylation mechanism. Furthermore genes homologous to alkysuccinate synthetases were not detected in the methanogenic hydrocarbon degrading community by pyrosequencing of total DNA extracted from methanogenic enrichments cultures. beta-oxidation genes were detected and intriguingly, alcohol and aldehyde dehydrogenase genes were present. This offers the possibility that alkane activation in the methanogenic system does not proceed via acid metabolites

  7. Cool Sooting Flames of Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    Z.A. MANSUROV

    2001-01-01

    This paper presents the study of polycyclic aromatic hydrocarbons (PAH) and paramagnetism of soot particles sampled from cool sooting flames of methane and propane in a separately-heated two-sectional reactor under atmospheric pressure at the reactor temperatures of 670-1170 K. The temperature profiles of the flames were studied. The sampling was carried out with a quartz sampler and the samples were frozen with liquid nitrogen. A number of polyaromatic hydrocarbons such as pyrene, fluoranthene, coronene, anthanthrene, 1,12-benzperylene,were identified by spectroscopic methods in the extract of soot. The processes of soot formation at methaneoxygen mixture combustion in the electric field with applied potential changed from 0 to 2,2 kV at different polarity of electrodes have been investigated. It has been stated that at the electrical field application, an increase in soot particle sizes and soot yield occurs; besides, at the application of the field, speeding up the positively charged particles, the interplanar distance decreases. On the basis of investigation of soot particles paramagnetism, it was shown that initially soot particles have high carcinogetic activity and pollute the environment owing to a rapid decrease of the number of these radical centers. The reduction of the radical concentration is connected with radical recombination on soot.

  8. 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.)

  9. 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.

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  14. 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...

  15. 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...

  16. 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.

  17. 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.

  18. 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.

  19. Molecular catalytic hydrogenation of aromatic hydrocarbons and hydrotreating of coal liquids.

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Shiyong; Stock, L.M.

    1996-05-01

    This report presents the results of research on the development of new catalytic pathways for the hydrogenation of multiring aromatic hydrocarbons and the hydrotreating of coal liquids at The University of Chicago under DOE Contract No. DE-AC22-91PC91056. The work, which is described in three parts, is primarily concerned with the research on the development of new catalytic systems for the hydrogenation of aromatic hydrocarbons and for the improvement of the quality of coal liquids by the addition of dihydrogen. Part A discusses the activation of dihydrogen by very basic molecular reagents to form adducts that can facilitate the reduction of multiring aromatic hydrocarbons. Part B examines the hydrotreating of coal liquids catalyzed by the same base-activated dihydrogen complexes. Part C concerns studies of molecular organometallic catalysts for the hydrogenation of monocyclic aromatic hydrocarbons under mild conditions.

  20. Anaerobic hydrocarbon and fatty acid metabolism by syntrophic bacteria and their impact on carbon steel corrosion

    Directory of Open Access Journals (Sweden)

    Christopher Neil Lyles

    2014-04-01

    Full Text Available The microbial metabolism of hydrocarbons is increasingly associated with the corrosion of carbon steel in sulfate-rich marine waters. However, how such transformations influence metal biocorrosion in the absence of an electron acceptor is not fully recognized. We grew a marine alkane-utilizing, sulfate-reducing bacterium, Desulfoglaeba alkanexedens, with either sulfate or Methanospirillum hungatei as electron acceptors, and tested the ability of the cultures to catalyze metal corrosion. Axenically, D. alkanexedens had a higher instantaneous corrosion rate and produced more pits in carbon steel coupons than when the same organism was grown in syntrophic co-culture with the methanogen. Since anaerobic hydrocarbon biodegradation pathways converge on fatty acid intermediates, the corrosive ability of a known fatty acid-oxidizing syntrophic bacterium, Syntrophus aciditrophicus was compared when grown in pure culture or in co-culture with a H2-utilizing sulfate-reducing bacterium (Desulfovibrio sp., strain G11 or a methanogen (M. hungatei. The instantaneous corrosion rates in the cultures were not substantially different, but the syntrophic, sulfate-reducing co-culture produced more pits in coupons than other combinations of microorganisms. Lactate-grown cultures of strain G11 had higher instantaneous corrosion rates and coupon pitting compared to the same organism cultured with hydrogen as an electron donor. Thus, if sulfate is available as an electron acceptor, the same microbial assemblages produce sulfide and low molecular weight organic acids that exacerbated biocorrosion. Despite these trends, a surprisingly high degree of variation was encountered with the corrosion assessments. Differences in biomass, initial substrate concentration, rates of microbial activity or the degree of end product formation did not account for the variations. We are forced to ascribe such differences to the metallurgical properties of the coupons.

  1. Anaerobic hydrocarbon and fatty acid metabolism by syntrophic bacteria and their impact on carbon steel corrosion.

    Science.gov (United States)

    Lyles, Christopher N; Le, Huynh M; Beasley, William Howard; McInerney, Michael J; Suflita, Joseph M

    2014-01-01

    The microbial metabolism of hydrocarbons is increasingly associated with the corrosion of carbon steel in sulfate-rich marine waters. However, how such transformations influence metal biocorrosion in the absence of an electron acceptor is not fully recognized. We grew a marine alkane-utilizing, sulfate-reducing bacterium, Desulfoglaeba alkanexedens, with either sulfate or Methanospirillum hungatei as electron acceptors, and tested the ability of the cultures to catalyze metal corrosion. Axenically, D. alkanexedens had a higher instantaneous corrosion rate and produced more pits in carbon steel coupons than when the same organism was grown in syntrophic co-culture with the methanogen. Since anaerobic hydrocarbon biodegradation pathways converge on fatty acid intermediates, the corrosive ability of a known fatty acid-oxidizing syntrophic bacterium, Syntrophus aciditrophicus was compared when grown in pure culture or in co-culture with a H2-utilizing sulfate-reducing bacterium (Desulfovibrio sp., strain G11) or a methanogen (M. hungatei). The instantaneous corrosion rates in the cultures were not substantially different, but the syntrophic, sulfate-reducing co-culture produced more pits in coupons than other combinations of microorganisms. Lactate-grown cultures of strain G11 had higher instantaneous corrosion rates and coupon pitting compared to the same organism cultured with hydrogen as an electron donor. Thus, if sulfate is available as an electron acceptor, the same microbial assemblages produce sulfide and low molecular weight organic acids that exacerbated biocorrosion. Despite these trends, a surprisingly high degree of variation was encountered with the corrosion assessments. Differences in biomass, initial substrate concentration, rates of microbial activity or the degree of end product formation did not account for the variations. We are forced to ascribe such differences to the metallurgical properties of the coupons.

  2. 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

  3. 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...

  4. 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.

  5. 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

  6. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

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

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin...

  7. 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.

  8. 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

  9. Some thoughts on the muon-catalyzed fusion process for antimatter propulsion and for the production of high A mass numbers antinuclei

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Hiroshi

    1987-01-01

    The muon-catalyzed fusion process has a very valuable role for antiproton science and technology. Several schemes of propulsion energy enhancement of the antiproton-fueled propulsion using the muon-catalyzed fusion are discussed. Production of high A mass antinuclei by the muon-catalyzed fusion using the clustered antihydrogen molecule and quark-gluon plasma formation by annihilation of the produced high A antimatter with regular nuclei are discussed. 22 refs., 2 figs., 1 tab.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. Characteristics and main controlling factors of hydrocarbon accumulation in Ordovician Yingshan Formation in Yubei area,Tarim Basin%塔里木盆地玉北地区奥陶系鹰山组油藏成藏特征及主控因素

    Institute of Scientific and Technical Information of China (English)

    谭广辉; 邱华标; 余腾孝; 刘少杰; 郝建龙

    2014-01-01

    Poor understanding of the main factors controlling hydrocarbon accumulation is the major constraint of petroleum exploration in Yubei area of Tarim Basin at present .The characteristics of hydrocarbon accumulation in Yubei 1 fault belt were studied .Oil reservoirs in the Ordovician Yingshan Formation in Yubei-1 wellblock are of karst-fractured vuggy type controlled by unconformity and related with paleo-karst of carbonate rocks .The reservoir spaces of the Yingshan Formation carbonates consist of pores ,vugs and fractures,and the reservoirs can be divided into 3 types,namely fractured-vuggy type, fractured type and vuggy type ,of which the fractured-vuggy type is the most significant in this area .The reservoir distribu-tion is mainly controlled by the karst of carbonate rocks .The reservoirs are characterized by strong heterogeneity ,vertical superimposition and lateral connection in large area ,as well as uneven oil-bearing property .The Yingshan Formation reser-voirs experienced multiple phases of hydrocarbon accumulation ,of which the Late Hercynian was the major one .Hydrocar-bon accumulation in the study area was jointly controlled by oil sources , reservoir , carrier system and cap rock .The oil sources were the foundation of hydrocarbon accumulation .The three-dimensional carrier network consisting of faults and un-conformities provided high quality pathway for hydrocarbon migration .The reservoir distribution controlled the formation of the pools and their scales .Mudstone intervals in the Lower and Middle Bachu Formation provided regional seals for the preservation of oil and gas .Based on the analysis of reservoir characteristics and controlling factors of hydrocarbon accumu -lation,we established a hydrocarbon accumulation pattern for the Yingshan Formation reservoirs in Yubei area .%油气成藏主控因素不明是目前制约玉北地区油气勘探的主要原因。玉北1断裂带成藏特征研究表明,玉北1井区奥陶系鹰山组油藏为

  15. 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

  16. 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

  17. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  18. Tailoring ZSM-5 Zeolites for the Fast Pyrolysis of Biomass to Aromatic Hydrocarbons

    DEFF Research Database (Denmark)

    Hoff, Thomas C.; Gardner, David W.; Thilakaratne, Rajeeva;

    2016-01-01

    The production of aromatic hydrocarbons from cellulose by zeolite-catalyzed fast pyrolysis involves a complex reaction network sensitive to the zeolite structure, crystallinity, elemental composition, porosity, and acidity. The interplay of these parameters under the reaction conditions represent...... a major roadblock that has hampered significant improvement in catalyst design for over a decade. Here, we studied commercial and laboratory-synthesized ZSM-5 zeolites and combined data from 10 complementary characterization techniques in an attempt to identify parameters common to high...

  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. 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.}

  1. 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.

  2. 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

  3. 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.

  4. Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

    DEFF Research Database (Denmark)

    Makarov, Ilya; Fristrup, Peter; Madsen, Robert

    2012-01-01

    The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

  5. 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

  6. 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)....

  7. Enzyme-catalyzed ring-opening polymerization of unsubstituted beta-lactam

    NARCIS (Netherlands)

    Schwab, Leendert W.; Kroon, Renee; Schouten, Arend Jan; Loos, Katja

    2008-01-01

    The synthesis of poly(beta-alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring-opening of 2-azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(beta-alanine) is obtained. The formation of the polymer is confi

  8. Synthesis of a Crushed Fullerene C60H24 through Sixfold Palladium‐Catalyzed Arylation

    Science.gov (United States)

    Dorel, Ruth; de Mendoza, Paula; Calleja, Pilar; Pascual, Sergio; González‐Cantalapiedra, Esther; Cabello, Noemí

    2016-01-01

    The synthesis of a new C 3v‐symmetric crushed fullerene C60H24 (5) has been accomplished in three steps from truxene through sixfold palladium‐catalyzed intramolecular arylation of a syn‐trialkylated truxene precursor. Laser irradiation of 5 induces cyclodehydrogenation processes that result in the formation of C60, as detected by LDI‐MS.

  9. Fe-Catalyzed Olefin Hydroamination with Diazo Compounds for Hydrazone Synthesis.

    Science.gov (United States)

    Zheng, Jing; Qi, Jifeng; Cui, Sunliang

    2016-01-01

    A novel Fe-catalyzed olefin hydroamination with diazo compounds for accessing hydrazones has been developed. Diazo compounds are used as radical acceptors and can be trapped by the in situ generated alkyl radical toward C-N bond formation. The reaction conditions are mild, and the substrate scope is broad. Additionally, this hydroamination protocol is applicable for intramolecular reactions to construct diverse heterocycles.

  10. Calculated molecular properties of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Hites, R.A.; Simonsick, W.J. Jr.

    1987-01-01

    This volume contains a compilation of calculated molecular properties for 272 polycyclic aromatic hydrocarbons (PAH) and monomethylated PAH, listed in sequence according to their increasing molecular weight. The Chemical Abstracts Registry number is also included for easy reference. The molecular properties were calculated using the semiempirical MDCO method with geometric optimization. These parameters include the heats of formation, the frontier orbital energies, the electronic and nuclear energies, the dipole moment, and the net atomic charges on each atom. The shape parameter and the length/breadth ratio from the optimized geometries is also computed.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. Polycyclic aromatic hydrocarbons (PAH) in Danish barbecued meat

    DEFF Research Database (Denmark)

    Duedahl-Olesen, Lene; Aaslyng, Margit Dall; Meinert, Lene;

    2015-01-01

    Barbecuing is known to result in the formation of polycyclic aromatic hydrocarbons (PAHs). A validated method that employed pressurized liquid extraction (PLE), gel permeation chromatography (GPC) followed by solid phase extraction (SPE) on Silica and analytical determination by GC-MS was applied...

  17. 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

  18. 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).

  19. Production of alkyl aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Bonacci, J.C.; Billings, R.P.

    1975-01-30

    An improved method is claimed for producing aromatic hydrocarbons from a hydrocarbon charge containing aromatic hydrocarbons including benzene and C/sub 8/ alkyl aromatics and aliphatic hydrocarbons which charge is rich in such aromatic hydrocarbons and lean in aliphatic hydrocarbons boiling above about 220/sup 0/F by reason of conversion under severe conditions which comprises subjecting said charge to distillation conditions of temperature and pressure such that at least a portion of the benzene content of said fraction is separated as vapor from an alkyl aromatic fraction containing aliphatic hydrocarbons and the major portion of C/sub 8/ aromatics in said charge, reacting said alkyl aromatic fraction in the presence of hydrogen in contact with a catalyst containing type ZSM-5 zeolite, zeolite ZSM-12, zeolite ZSM-21 or zeolite beta in combination with a hydrogenation/dehydrogenation component at conversion conditions to convert aliphatic hydrocarbons to lower boiling material of five carbon atoms and lighter separable from aromatics by distillation including a temperature of about 500/sup 0/ to 1000/sup 0/F, a pressure of about 100 to about 600 pounds, a hydrogen to hydrocarbon mol ratio of 0.2 to 8 and weight hourly space velocity of 0.5 to 15, concurrently contacting a mixture of hydrogen and toluene with a disproportionation catalyst under reaction conditions to disproportionate said toluene, combining the effluents of said contacting steps, separating hydrogen from the combined effluents of said contacting steps, separating hydrogen from the combined effluents, recycling at least a portion of said separated hydrogen to said contacting steps, distilling the hydrocarbon residue from said separation step to recover therefrom at least toluene and mixed xylenes, and recycling at least a portion of said recovered toluene as feed to the disproportionation step aforesaid.

  20. 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 ...

  1. 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 ...

  2. 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

  3. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. PMID:27431372

  4. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products.

  5. 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...

  6. 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 metal...... ion binding sites, one of which is occupied in the mononuclear species. In this work it is assumed that catalysis takes place at zinc site 1, which is modeled by the metal ion, three imidazole rings, and a hydroxide ion. The lactam ring, a minimal model of beta-lactam antibiotics, is initially...... coordinating to the zinc ion. Potential proton shuttles from the second (unoccupied) metal-binding site (water, Asp, or Cys) are included in some calculations. The calculated reaction barrier for formation of the tetrahedral intermediate is 13 kcal/mol, close to what is observed experimentally for the rate...

  7. Muon Catalyzed Fusion in 3 K Solid Deuterium

    CERN Document Server

    Knowles, P E; Bailey, J M; Beer, G A; Beveridge, J L; Fujiwara, M C; Huber, T M; Jacot-Guillarmod, R; Kammel, P; Kim, S K; Kunselman, A R; Marshall, G M; Martoff, C J; Mason, G R; Mulhauser, F; Olin, A; Petitjean, C; Porcelli, T A; Zmeskal, J; Zmeskal, and J.

    1997-01-01

    Muon catalyzed fusion in deuterium has traditionally been studied in gaseous and liquid targets. The TRIUMF solid-hydrogen-layer target system has been used to study the fusion reaction rates in the solid phase of D_2 at a target temperature of 3 K. Products of two distinct branches of the reaction were observed; neutrons by a liquid organic scintillator, and protons by a silicon detector located inside the target system. The effective molecular formation rate from the upper hyperfine state of $\\mu d$ and the hyperfine transition rate have been measured: $\\tilde{\\lambda}_(3/2)=2.71(7)_{stat.}(32)_{syst.} The molecular formation rate is consistent with other recent measurements, but not with the theory for isolated molecules. The discrepancy may be due to incomplete thermalization, an effect which was investigated by Monte Carlo calculations. Information on branching ratio parameters for the s and p wave d+d nuclear interaction has been extracted.

  8. 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.

  9. 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.

  10. 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

  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. 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

  14. 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...

  15. 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

  16. 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)

  17. 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.

  18. 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.

  19. Identification of some novel tetracyclic diterpene hydrocarbons in petroleum

    Energy Technology Data Exchange (ETDEWEB)

    Petrov, A.A.; Pehk, T.Y.; Vorobieva, N.S.; Zemskova, Z.K. (Institute of Geology and Exploitation of Combustible Minerals, Moscow (USSR))

    1988-01-01

    A new group of tetracyclic diterpene hydrocarbons of molecular formula C{sub 19}H{sub 32} has been found in the Jurassic oils and condensates of the Central Kara-Kum (Turkmenia, U.S.S.R.). The structure of the hydrocarbons has been determined by gas chromatography-mass spectrometry and {sup 1}H and {sup 13}C NMR. Of the compounds identified 4,8-dimethyl-13-isopropyltetracyclo(6.6.0.0{sup 1,11}O{sup 3,7})- and 5,14-dimethyl-10-isopropyltetracyclo = (6.4.1.1.{sup 1,9}O{sup 4,13})tetradecanes are present in the highest concentrations. Some ideas are put forward about the source and the reactions involved in the formation of the hydrocarbons under natural conditions by the enzymic C{sub 5} cyclization of aliphatic isoprenoids.

  20. Main Controls on Hydrocarbon Accumulation in the Paleozoic in Central Saudi Arabia

    Institute of Scientific and Technical Information of China (English)

    Bai Guoping

    2007-01-01

    Saudi Arabia is renown for its rich oil and gas resources with the bulk of the reserves reservoired in the Mesozoic.However,the discovery of Paleozoic fields in the late 1980s has encouraged further exploration in the Paleozoic.This paper reviews the salient features of the Paleozoic petroleum geology in central Saudi Arabia and discusses the main factors controlling hydrocarbon accumulation in the Paleozoic.The Lower Silurian Qusaiba hot shale is the principal source rock for the hydrocarbons discovered in the Ordovician to Permian reservoirs.Of them,the Permo-Carboniferous Unayzah and Upper Ordovician Sarah Formations have the best exploration potential.The key factors controlling hydrocarbon accumulation in the Unayzah Formation are migration pathways and reservoir petrophysics.The key factors controlling hydrocarbon accumulation in the Sarah Formation are reservoir petrophysics and the development of structural traps.

  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. 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.

  3. 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.

  4. Crossed beam reaction of cyano radicals with hydrocarbon molecules. IV. Chemical dynamics of cyanoacetylene (HCCCN; X 1Σ+) formation from reaction of CN(X 2Σ+) with acetylene, C2H2(X 1Σg+)

    Science.gov (United States)

    Huang, L. C. L.; Asvany, O.; Chang, A. H. H.; Balucani, N.; Lin, S. H.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.

    2000-11-01

    The chemical reaction dynamics to form cyanoacetylene, HCCCN (X 1Σ+), via the radical-neutral reaction of cyano radicals, CN(X 2Σ+;ν=0), with acetylene, C2H2(X 1Σg+), are unraveled in crossed molecular beam experiments at two collision energies of 21.1 and 27.0 kJ mol-1. Laboratory angular distributions and time-of-flight spectra of the HCCCN product are recorded at m/e=51 and 50. Experiments were supplemented by electronic structure calculations on the doublet C3H2N potential energy surface and RRKM investigations. Forward-convolution fitting of the crossed beam data combined with our theoretical investigations shows that the reaction has no entrance barrier and is initiated by an attack of the CN radical to the π electron density of the acetylene molecule to form a doublet cis/trans HCCHCN collision complex on the 2A' surface via indirect reactive scattering dynamics. Here 85% of the collision complexes undergo C-H bond rupture through a tight transition state located 22 kJ mol-1 above the cyanoacetylene, HCCCN (X 1Σ+) and H(2S1/2) products (microchannel 1). To a minor amount (15%) trans HCCHCN shows a 1,2-H shift via a 177 kJ mol-1 barrier to form a doublet H2CCCN radical, which is 46 kJ mol-1 more stable than the initial reaction intermediate (microchannel 2). The H2CCCN complex decomposes via a rather loose exit transition state situated only 7 kJ mol-1 above the reaction products HCCCN (X 1Σ+) and H(2S1/2). In both cases the geometry of the exit transition states is reflected in the observed center-of-mass angular distributions showing a mild forward/sideways peaking. The explicit identification of the cyanoacetylene as the only reaction product represents a solid background for the title reaction to be included in reaction networks modeling the chemistry in dark, molecular clouds, outflow of dying carbon stars, hot molecular cores, as well as the atmosphere of hydrocarbon rich planets and satellites such as the Saturnian moon Titan.

  5. Review of current research on hydrocarbon production by plants

    Energy Technology Data Exchange (ETDEWEB)

    Benedict, H. M.; Inman, B.

    1979-01-01

    This review assesses the status of research and development in the area of plants that produce hydrocarbons as a possible replacement for traditional fossil fuels. The information is meant to be used as a basis for determining the scope of a possible R and D program by DOE/FFB. Except in the case of guayule (Parthenium argentatum Gray), research on hydrocarbon species generally has not advanced beyond preliminary screening, extraction, and growth studies. Virtually no field studies have been initiated; hydrocarbon component extraction, separation, identification, and characterization have been only timidly approached; the biochemistry of hydrocarbon formation remains virtually untouched; and potential market analysis has been based on insufficient data. Research interest is increasing in this area, however. Industrial interest understandably centers about guayule prospects and is supplemented by NSF and DOE research funds. Additional support for other research topics has been supplied by DOE and USDA and by certain university systems. Due to the infant state of technology in this area of energy research, it is not possible to predict or satisfactorily assess at this time the potential contribution that plant hydrocarbons might make toward decreasing the nation's dependence upon petroleum. However, the general impression received from experts interviewed during this review was that the major thrust of research should be directed toward the manufacture of petrochemical substitutes rather than fuel production.

  6. 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)

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

    Science.gov (United States)

    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 synthesis is, therefore, a reaction in reverse way of in vivo lipase catalysis of ester bond-cleavage with hydrolysis. The lipase-catalyzed polymerizations show very high chemo-, regio-, and enantio-selectivities and involve various advantageous characteristics. Lipase is robust and compatible with other chemical catalysts, which allows novel chemo-enzymatic processes. New syntheses of a variety of functional polyesters and a plausible reaction mechanism of lipase catalysis are mentioned. The polymerization characteristics are of green nature currently demanded for sustainable society, and hence, desirable for conducting ‘green polymer chemistry’. PMID:20431260

  8. 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.

  9. 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...

  10. 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...

  11. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.

  12. Data, Leadership, and Catalyzing Culture Change

    Science.gov (United States)

    Benson, R. Todd; Trower, Cathy A.

    2012-01-01

    It is crucial to understand today's tenure-track workers so that colleges and universities can continue to attract and retain a large subset of them by understanding and supporting their satisfaction and success at work. In this article, the authors talk about data, leadership, and catalyzing culture change. They discuss data use in the academy…

  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. Rhodium-catalyzed restructuring of carbon frameworks.

    Science.gov (United States)

    Murakami, Masahiro

    2010-10-01

    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products.

  15. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid. PMID:25668586

  16. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    Science.gov (United States)

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  17. 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.

  18. 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.

  19. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    Institute of Scientific and Technical Information of China (English)

    Wang Hai-Feng; Lin Zhen-Quan; Gao Yan

    2008-01-01

    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 < 0 case, the irreversible aggregation dominates the process, and ak(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. The Deceptively Simple Thermolysis of Trivalent Permethyltitanocene Derivatives (η5-C5Me5)2TiR. Formation of a Tetramethylfulvene Titanium Compound (η6-C5Me4CH2)(η5-C5Me5)Ti and RH, Catalyzed by Permethyltitanocene Hydride, (η5-C5Me5)2TiH

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.

    1992-01-01

    The complexes Cp*2TiR (Cp* = η5-C5Me5; R = Me, Et, n-Pr, C2H3, CH2CMe3, Ph) undergo thermolysis to yield the fulvene complex Cp*FvTi (Fv = η6-C5Me4CH2) and RH. Kinetic measurements and deuterium labeling studies show that the decomposition is catalyzed by Cp*2TiH, which is formed either by β-hydroge

  1. 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)

  2. 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)

  3. 走滑断裂与盖层复合成藏模式--以塔中东部中古51井区鹰山组为例%Hydrocarbon accumulation pattern jointly controlled by strike-slip faults and cap rocks:a case from Yingshan Formation in ZG-51 wellblock of eastern Tazhong area,Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    兰晓东; 吕修祥; 朱炎铭; 李世银; 谢恩

    2014-01-01

    Oil/gas/water distribution is complex in the marine carbonate reservoirs of the Yingshan Formation in ZG-51 well-block of eastern Tazhong area .Based on analysis of the existing oil and gas exploration results ,fault characteristics and reser-voir-seal assemblage ,we studied the oil/gas distribution and accumulation characteristics of the Yingshan Formation by using various data such as routine logging ,image logging ,seismic data and geochemical data .The reservoirs of Yingshan Formation in this wellblock are predominantly of vuggy type and fractured-vuggy type,and show quasi-layer distribution along unconformi-ties.The strike-slip faults significantly controlled hydrocarbon accumulation .The distance between oil/gas wells and major strike-slip faults ranges from 0.5 to 4.0 km.The daily oil and gas output decreases away from the strike-slip faults.The geo-chemical behaviors of oil and gas also changes regularly with the distance to the strike-slip faults.In plane view,the gas reser-voirs are near the faults,while oil reservoirs are far from these faults .The 3rd to 5th members of Lianglitag Formation as well as the high resistive intervals of the Yingshan Formation act as barriers .Vertically,multiple reservoir-seal combinations superim-pose each other,resulting in oil/gas accumulation in multiple layers .The early oil pools were influenced by gas invasion in later stage ,resulting in the vertical distribution characteristics of “upper oil and lower gas”.Hydrocarbons accumulated in favorable structural traps and lithologic traps under the jointly control of cap rocks and strike -slip faults.%塔中地区东部中古51井区鹰山组碳酸盐岩油、气、水分布复杂。为探求鹰山组油气分布及成藏特征,通过对现有油、气、水勘探成果、断裂特征及储盖组合进行分析,应用常规测井、成像测井、地震及地化等多种方法开展研究。研究表明,该井区鹰山组储层以孔洞型和裂缝-孔洞型为

  4. 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.

  5. FBH1 Catalyzes Regression of Stalled Replication Forks

    Directory of Open Access Journals (Sweden)

    Kasper Fugger

    2015-03-01

    Full Text Available DNA replication fork perturbation is a major challenge to the maintenance of genome integrity. It has been suggested that processing of stalled forks might involve fork regression, in which the fork reverses and the two nascent DNA strands anneal. Here, we show that FBH1 catalyzes regression of a model replication fork in vitro and promotes fork regression in vivo in response to replication perturbation. Cells respond to fork stalling by activating checkpoint responses requiring signaling through stress-activated protein kinases. Importantly, we show that FBH1, through its helicase activity, is required for early phosphorylation of ATM substrates such as CHK2 and CtIP as well as hyperphosphorylation of RPA. These phosphorylations occur prior to apparent DNA double-strand break formation. Furthermore, FBH1-dependent signaling promotes checkpoint control and preserves genome integrity. We propose a model whereby FBH1 promotes early checkpoint signaling by remodeling of stalled DNA replication forks.

  6. 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

  7. Enrichment of light hydrocarbon mixture

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Dali (Los Alamos, NM); Devlin, David (Santa Fe, NM); Barbero, Robert S. (Santa Cruz, NM); Carrera, Martin E. (Naperville, IL); Colling, Craig W. (Warrenville, IL)

    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.

  8. Hydrocarbon components in carbonaceous meteorites

    Science.gov (United States)

    Kissin, Y. V.

    2003-05-01

    Currently, the presence of free n-alkanes and isoprenoid alkanes in carbonaceous meteorites is usually explained either by microbial contamination during the period between the meteorite fall and collection or by contamination from the environment of analytical laboratories and museums. The goal of this research was to repeat analysis of hydrocarbon components in meteorites and to investigate possible meteorite contamination routes discussed in the literature. Experimental analysis of free organic constituents in five carbonaceous meteorites by infrared spectroscopy (IR) and gas chromatographic (GC) methods confirmed the presence of extractable aliphatic components, n-alkanes in the C 15H 32-C 27H 56 range and isoprenoid alkanes (phytane, pristane, and norpristane), in some of these meteorites. The contents of these compounds vary depending on the source. Insoluble organic components of two meteorites (meteorite kerogens) were isolated, and their composition was analyzed by IR and cracking/GC methods. Comparison with the data on several terrestrial contamination sources proposed in the literature shows that the presence of free saturated hydrocarbons in meteorites and the composition of the meteorite kerogen could not be explained either by microbial contamination or by contamination from the laboratory environment. The types of the hydrocarbons in meteorites resemble those typical of ancient terrestrial deposits of organic-rich sediments, except for the absence of lighter hydrocarbons, which apparently slowly evaporated in space, and multi-ring naphthenic compounds of the biologic origin, steranes, terpanes, etc. The prevailing current explanation for the presence of free linear saturated hydrocarbons in carbonaceous meteorites, apart from contamination, is the abiotic route from hydrogen and carbon monoxide. However, the data on the structure of meteorite kerogens require a search for different routes that initially produce complex polymeric structures containing

  9. 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

  10. 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)

  11. 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

  12. 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.

  13. Acid-catalyzed hydrogenation of olefins. A theoretical study of the HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Siria, J.C.; Duran, M.; Lledos, A.; Bertran, J.

    1987-12-09

    The HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene and the direct addition of molecular hydrogen to ethylene have been studied theoretically by means of ab initio MO calculations using different levels of theory. The main results are that catalysis by HF lowers the potential energy barrier to a large extent, while catalysis by H/sub 3/O/sup +/ diminishes dramatically the barrier for the reaction. Entropic contributions leave these results unchanged. The mechanisms of the two acid-catalyzed hydrogenations are somewhat different. While catalysis by HF exhibits bifunctional characteristics, catalysis by H/sub 3/O/sup +/ proceeds via an initial formation of a carbocation. It is shown that catalysis by strong acids may be an alternate way for olefin hydrogenation.

  14. Suppression of Lipid Accumulation by Indole-3-Carbinol Is Associated with Increased Expression of the Aryl Hydrocarbon Receptor and CYP1B1 Proteins in Adipocytes and with Decreased Adipocyte-Stimulated Endothelial Tube Formation

    Science.gov (United States)

    Wang, Mei-Lin; Lin, Shyh-Hsiang; Hou, Yuan-Yu; Chen, Yue-Hwa

    2016-01-01

    This study investigated the effects of indole-3-carbinol (I3C) on adipogenesis- and angiogenesis-associated factors in mature adipocytes. The cross-talk between mature adipocytes and endothelial cells (ECs) was also explored by cultivating ECs in a conditioned medium (CM) by using I3C-treated adipocytes. The results revealed that I3C significantly inhibited triglyceride accumulation in mature adipocytes in association with significantly increased expression of AhR and CYP1B1 proteins as well as slightly decreased nuclear factor erythroid-derived factor 2–related factor 2, hormone-sensitive lipase, and glycerol-3-phosphate dehydrogenase expression by mature adipocytes. Furthermore, I3C inhibited CM-stimulated endothelial tube formation, which was accompanied by the modulated secretion of angiogenic factors in adipocytes, including vascular endothelial growth factor, interleukin-6, matrix metalloproteinases, and nitric oxide. In conclusion, I3C reduced lipid droplet accumulation in adipocytes and suppressed adipocyte-stimulated angiogenesis in ECs, suggesting that I3C is a potential therapeutic agent for treating obesity and obesity-associated disorders. PMID:27527145

  15. 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

  16. 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...

  17. 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 ...

  18. Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of Unsaturated Carbohydrates.

    Science.gov (United States)

    Bender, Trandon A; Dabrowski, Jennifer A; Zhong, Hongyu; Gagné, Michel R

    2016-08-19

    A B(C6F5)3-catalyzed method for the selective conversion of unsaturated carbohydrates to cyclopentanes and cyclopropanes is disclosed. Catalyst activation of tertiary silanes generates the ion pair [(C6F5)3B-H][ROSi2] whose components synergistically activate C-O bonds for diastereoselective C-C bond formation. Sila-THF cations are invoked as key intermediates facilitating carbocyclizations. Complex chiral synthons are thereby obtained in a single pot.

  19. 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 ...

  20. The intriguing modeling of cis–trans selectivity in ruthenium-catalyzed olefin metathesis

    Directory of Open Access Journals (Sweden)

    Luigi Cavallo

    2011-01-01

    Full Text Available In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed.

  1. The intriguing modeling of cis–trans selectivity in ruthenium-catalyzed olefin metathesis

    Science.gov (United States)

    Bahri-Laleh, Naeimeh; Credendino, Raffaele

    2011-01-01

    Summary In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM) of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed. PMID:21286393

  2. 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 ...

  3. 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.

  4. 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...

  5. 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

  6. 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

  7. Treating tar sands formations with dolomite

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. 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...

  9. Formation evolution and control of hydrocarbon accumulation in north part of Tianjing mountain in Long-men%龙门山北段天井山构造演化及其对油气聚集的控制

    Institute of Scientific and Technical Information of China (English)

    李卿; 李忠权; 张玮; 刘爱疆; 曾吉和; 崔文玲

    2013-01-01

    龙门山褶皱冲断带位于四川克拉通以东,被围限在扬子、华北和羌塘三大陆块拼贴构造间.以全工区地震精细解释为基础,结合野外调查,选取近东西向的剖面06fsc0003-02tjs1111线,利用平衡剖面法恢复天井山构造带的造山过程.结果表明:天井山构造带的演化可划分为伸展拉张成盆阶段(震旦纪—中三叠世末)、陆隆伸展演化阶段(晚三叠世—中侏罗世末)、挤压抬升剥蚀阶段(晚侏罗世—现今)3期.根据生储盖组合和油气运移条件,认为自元古代以来最大主应力性质发生多次改变,控制构造变形、生储盖组合分布及厚度、断裂特征和油气运聚.印支期冲断带下盘(现今天井山背斜前翼下部)发育形成于印支期晚期的冲起构造,其内断层发育,将二叠系、志留系及寒武系烃源岩与二叠系储层和圈闭串通,有利于烃类的运聚,且有飞仙关组泥岩作为直接盖层,保存条件较好,是油气集聚的有利部位.该研究能够加深对龙门山褶皱冲断带油气分布预测的认识,对油气勘探具有指导意义.%Interpretation of the whole work area seismologic, combined with well drilling and field survey, we selected east-west profile of line 06fsc0003—02tjsllll. The evolution of Tianjing Mountain region can be regarded as being divided into four stages: stretching basin—formation (Sinian-Terminal Middle Triassic), continental emergence stretching evolution stage (Late Triassic-Terminal Middle Jurassic), lifting and denudation stage (Late Jurassic-Terminal Early Cretaceous) and reformation succession stage (LateCretaceous-Present). The conditions about the migration of oil and gas and the combinations of source rock, reservoir and cap rock are analyzed. The faults are believed to be developed which existed in the heading side which was formed in the later period of Indonesia epoch. Due to the existence of faults, the oil trapsand resource rock is connected, which

  10. 欠压实泥岩顶底板形成机理及其对油气运移的影响%Formation Mechanism of the Undercompacting Mudstone's Roof and Floor and Their Influence on Hydrocarbon Migration

    Institute of Scientific and Technical Information of China (English)

    冯冲; 邹华耀; 汪斌

    2012-01-01

    欠压实泥岩顶底板是指比中部欠压实泥岩较致密的泥岩表层,是趋于正常压实的泥岩层,发育于低渗透率的厚层泥岩的上、下部位.以低速渗流定律为理论基础,从微观机理上分析欠压实泥岩顶底板的形成过程,提出穿过欠压实泥岩顶底板流体运移阻力的计算公式.当含顶底板泥岩作为盖层时,分为连续沉积型、抬升型和压裂型3种.压裂型泥岩盖层的封闭能力等于底板排替压力与达到顶板破裂的剩余压力之和,其他两种盖层的封闭能力就等于盖层顶底板的排替压力之和.当含顶底板泥岩作为源岩时,在连续型源岩中,油气排放的方向主要取决于泥岩顶底板渗透性地层的发育程度;在压裂型源岩中,大量油气沿裂缝向上排烃.此外,源岩的排烃方向还受断层的控制.通过欠压实泥岩顶底板形成机理的研究,有助于评价泥岩盖层的封烃能力,了解泥质烃源岩油气初次运移的方向.%Undercompacting mudstone's roof and floor (UMRF) are the mudstone surface layers that are tighter than the central undercompaction, and are close to the normal compacting mudstone. UMRF develops in upper and lower parts of thick-layered mudstone with low permeability. This paper, by the Laws of Low-speed Flow, analyzed formation process of the UMRF from the microscopic mechanism, and proposed the resistance force formula of the fluid passing UMRF. The mudstone with the UMRF as a cap rock, can be divided into three types; the continuous sedimentary type, the uplift type and the fracture type. The sealing ability of the fracture type mudstone cap rock is equal to the floor's displacement pressure plus the roofs overpressure when it breaks down. The other two types of mudstone cap rocks' sealing abilities are equal to the floor's displacement pressure plus the roofs displacement pressure. When the mudstone with the UMRF as a source rock, in the continuous type, the expulsion direction

  11. 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...

  12. 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.

  13. 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...

  14. Fire-safe hydrocarbon fuels

    Energy Technology Data Exchange (ETDEWEB)

    Fodor, G.E.; Weatherford, W.D. Jr.; Wright, B.R.

    1979-11-06

    A stabilized, fire-safe, aqueous hydrocarbon fuel emulsion prepared by mixing: a diesel fuel; an emulsifier (consisting of oleyl diethanolamide, diethanolamine, and diethanolamine soap of oleic acid) which has been treated with about 0 to 7 1/2 of oleic acid. A modified version of this fuel also contains 0 to 0.5% of an antimisting agent, and water.

  15. Modular Copper-Catalyzed Synthesis of Chromeno[4,3-b]quinolines with the Utilization of Diaryliodonium Salts.

    Science.gov (United States)

    Aradi, Klára; Bombicz, Petra; Novák, Zoltán

    2016-02-01

    A novel, highly modular synthetic method with high functional group tolerance was developed for the construction of chromenoquinoline derivatives from arylpropynyloxy-benzonitriles and diaryliodonium triflates via an oxidative arylation-cyclization path. The copper(I) chloride catalyzed reaction is presumed to involve the formation of highly active arylcopper(III) species.

  16. 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

  17. Characteristics of hydrocarbon source rocks in Amushan Formation in Manghanchaoke region of Alxa Right Banner, western Inner Mongolia%内蒙古西部阿拉善右旗芒罕超克地区上石炭统一下二叠统阿木山组烃源岩的特征

    Institute of Scientific and Technical Information of China (English)

    魏仙样; 陈高潮; 魏建设; 李玉宏

    2011-01-01

    对芒罕超克地区阿木山组(C2P1a)岩性组合与沉积相纵向发育特征研究,结合区域沉积相展布分析,认为阿木山组沉积期为巴丹吉林海相裂谷盆地发育的鼎盛时期,沉积了一套厚度巨大的浅海陆棚相泥页岩,是区内烃源岩发育的主要层段.以TOC≥0.3%为下限,折算烃源岩厚度121.39m.其中,TOC含量中等-较高的烃源岩厚度达89.11m,占烃源岩分布层段厚度的58.9%;干酪根C同位素、甾烷C27与C29相对含量、饱和烃特征等地球化学指标研究表明,干酪根类型以Ⅱ型为主;姥鲛烷(Pr)/植烷(Pb)所反映的原始沉积环境表明,有机质沉积环境主要为还原环境,对有机质保存有利;镜质组反射率、最大热解温度和伊利石结晶度分析表明,烃源岩演化进入过成熟阶段,主要受构造动力作用和华力西晚期、印支期岩浆热接触作用的影响,不存在区域变质,不影响区域上阿木山组作为重要的烃源岩层段.%Based on a study of the lithologic association, vertical characteristics of sedimentary facies and regional sedimentary distribution of Amushan Formation in Manghanchaoke region, the authors hold that the flourishing period of Badanjilin marine rift basin was the sedimentary period of Amushan Formation, during which the shallow marine shelf facies mud shale of huge sedimentary thickness was deposited, which constitutes the main layer section of source rocks in this region. With TOC ≥0.3% as the lower limit, the converted thickness of the source rock is 121.39m, in which the thickness of middle to higher organic carbon is 89.11m,possessing 58.9% of the thickness of the hydrocarbon source rock layer. A study of geochemical indexes of kerogen carbon isotopes, the relative content of C27 & C29 sterane and saturation hydrocarbon characteristics shows that the main kerogen type is Ⅱ type. An analysis of original sedimentary environment with Pr/Ph shows that the main sedimentary environment

  18. 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.

  19. 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...

  20. 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).

  1. 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.

  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. 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.

  4. 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.

  5. Comprehensive geochemical identification of highly evolved marine hydrocarbon source rocks: Organic matter, paleoenvironment and development of effective hydrocarbon source rocks

    Institute of Scientific and Technical Information of China (English)

    TENGER; LIU Wenhui; XU Yongchang; CHEN Jianfa; HU Kai; GAO Changlin

    2006-01-01

    This study analyzed the developing environments of hydrocarbon source rocks in the Ordos Basin and evaluated carbonate rocks as hydrocarbon source rocks and their distributions on account of the fact that China's marine carbonate rocks as hydrocarbon source rocks are characterized by the intensive thermal evolution and relatively low abundance of organic matter, by taking the Lower Paleozoic of the Ordos Basin for example and in light of the calculated enrichment coefficients of trace elements, the profile analysis of trace element contents, ratios of relevant elements, and stable isotopic compositions and their three-dimensional diagrammatization in combination with the necessary organic parameters. As for the Ordos Basin, TOC=0.2% is an important boundary value. Studies have shown that in the strata TOC>0.2%, V/(V+Ni)>0.50, Zr/Rb<2, Rb/K(×104)>30, Z>122, Th/U>0.80, Zn and Mo are enriched with a positive δ13Ccarb excursion. All these indicated a stagnant and stratified sedimentary environment that has low energy, anoxia and high salinity in bottom water. In these strata the geological conditions are good for the preservation of organic matter, hence favoring the development of hydrocarbon source rocks. These strata have δ13Corg<-28‰ (Ⅰ-Ⅱtype) and high hydrocarbon-generated potential. The Klimory and Wulalik formations show certain regularities in those aspects, therefore, they can be regarded as the potential effective hydrocarbon source rocks. In the strata TOC≤0.2%, Zr/Rb>1, V/(V+Ni)<0.50, Rb/K<30, Th/U<0.80, Cu, Zn, etc are depleted, and δ13Corg values range from -24‰ to -28‰. All these facts showed that most of the carbonate rocks or mudstones were formed in high-energy oxidizing environments, thus unfavorable to the development of hydrocarbon source rocks. It is feasible to make use of the geochemical method to comprehensively assess the highly evolved marine carbonates rocks as potential hydrocarbon source rocks and

  6. The general base in the thymidylate synthase catalyzed proton abstraction.

    Science.gov (United States)

    Ghosh, Ananda K; Islam, Zahidul; Krueger, Jonathan; Abeysinghe, Thelma; Kohen, Amnon

    2015-12-14

    The enzyme thymidylate synthase (TSase), an important chemotherapeutic drug target, catalyzes the formation of 2'-deoxythymidine-5'-monophosphate (dTMP), a precursor of one of the DNA building blocks. TSase catalyzes a multi-step mechanism that includes the abstraction of a proton from the C5 of the substrate 2'-deoxyuridine-5'-monophosphate (dUMP). Previous studies on ecTSase proposed that an active-site residue, Y94 serves the role of the general base abstracting this proton. However, since Y94 is neither very basic, nor connected to basic residues, nor located close enough to the pyrimidine proton to be abstracted, the actual identity of this base remains enigmatic. Based on crystal structures, an alternative hypothesis is that the nearest potential proton-acceptor of C5 of dUMP is a water molecule that is part of a hydrogen bond (H-bond) network comprised of several water molecules and several protein residues including H147, E58, N177, and Y94. Here, we examine the role of the residue Y94 in the proton abstraction step by removing its hydroxyl group (Y94F mutant). We investigated the effect of the mutation on the temperature dependence of intrinsic kinetic isotope effects (KIEs) and found that these KIEs are more temperature dependent than those of the wild-type enzyme (WT). These results suggest that the phenolic -OH of Y94 is a component of the transition state for the proton abstraction step. The findings further support the hypothesis that no single functional group is the general base, but a network of bases and hydroxyls (from water molecules and tyrosine) sharing H-bonds across the active site can serve the role of the general base to remove the pyrimidine proton.

  7. 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

  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. Importance of Vanadium-Catalyzed Oxidation of SO2to SO3in Two-Stroke Marine Diesel Engines

    DEFF Research Database (Denmark)

    Colom, Juan M.; Alzueta, María U.; Christensen, Jakob Munkholt;

    2016-01-01

    Low-speed marine diesel engines are mostly operated on heavy fuel oils, which have a high content of sulfur andash, including trace amounts of vanadium, nickel, and aluminum. In particular, vanadium oxides could catalyze in-cylinderoxidation of SO2 to SO3, promoting the formation of sulfuric acid...... of the catalyticspecies within the engine. Experiments with different particle compositions (vanadium/sodium ratio) and temperatures (300−800 °C) show that both the temperature and sodium content have a major impact on the oxidation rate. Kinetic parameters forthe catalyzed reaction are determined, and the proposed...

  10. Calcium-Catalyzed, Dehydrative, Ring-Opening Cyclizations of Cyclopropyl Carbinols Derived from Donor-Acceptor Cyclopropanes.

    Science.gov (United States)

    Sandridge, Matthew J; France, Stefan

    2016-09-01

    A calcium-catalyzed, dehydrative, ring-opening cyclization of (hetero)aryl cyclopropyl carbinols is reported. The cyclopropyl carbinols are prepared directly from the corresponding donor-acceptor (D-A) cyclopropanes. The calcium catalyst catalyzes the formation of putative (hetero)aryl cyclopropyl carbinyl cations that undergo ring-opening to allylcarbinyl cations. Subsequent intramolecular Friedel-Crafts reaction affords (hetero)aryl-fused cyclohexa-1,3-dienes in up to 97% yield. This approach represents the first example of catalysis for this intramolecular, dehydrative ring-opening cyclization and outperforms the previous reports using stoichiometric Lewis acids. PMID:27517711

  11. 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.

  12. 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.

  13. Hydrocarbon conversion with ZSM-12

    Energy Technology Data Exchange (ETDEWEB)

    Rosinski, E.J.; Rubin, M.K.

    1976-07-20

    The specification discloses conversion of hydrocarbons using, as catalyst, a crystalline zeolite designated ZSM-12. The zeolite has the following composition: 1,0 +- 0.4 M/sub 2/O . W/sub 2/O . 20-200 YO/sub 2/ . ZH/sub 2/O where M is at least one cation and n is the valence thereof, W is aluminum or gallium, Y is silicon or germanium, and Z is a value ranging from 0 to 60. In a preferred synthesized form, M is a mixture of alkali metal cations, especially sodium, and tetraalkylammonium cations. These zeolites are characterized by a specified x-ray powder diffraction pattern. Catalytically-active forms of said zeolites are used in a wide variety of hydrocarbon conversion reactions.

  14. 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

  15. 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.

  16. 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

  17. 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...

  18. 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.

  19. 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

  20. Abnormal pressure in hydrocarbon environments

    Science.gov (United States)

    Law, B.E.; Spencer, C.W.

    1998-01-01

    Abnormal pressures, pressures above or below hydrostatic pressures, occur on all continents in a wide range of geological conditions. According to a survey of published literature on abnormal pressures, compaction disequilibrium and hydrocarbon generation are the two most commonly cited causes of abnormally high pressure in petroleum provinces. In young (Tertiary) deltaic sequences, compaction disequilibrium is the dominant cause of abnormal pressure. In older (pre-Tertiary) lithified rocks, hydrocarbon generation, aquathermal expansion, and tectonics are most often cited as the causes of abnormal pressure. The association of abnormal pressures with hydrocarbon accumulations is statistically significant. Within abnormally pressured reservoirs, empirical evidence indicates that the bulk of economically recoverable oil and gas occurs in reservoirs with pressure gradients less than 0.75 psi/ft (17.4 kPa/m) and there is very little production potential from reservoirs that exceed 0.85 psi/ft (19.6 kPa/m). Abnormally pressured rocks are also commonly associated with unconventional gas accumulations where the pressuring phase is gas of either a thermal or microbial origin. In underpressured, thermally mature rocks, the affected reservoirs have most often experienced a significant cooling history and probably evolved from an originally overpressured system.

  1. $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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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

  13. 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.

  14. HYDROCARBON AND SULFUR SENSORS FOR SOFC SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    A.M. Azad; Chris Holt; Todd Lesousky; Scott Swartz

    2003-11-01

    The following report summarizes work conducted during the Phase I program Hydrocarbon and Sulfur Sensors for SOFC Systems under contract No. DE-FC26-02NT41576. For the SOFC application, sensors are required to monitor hydrocarbons and sulfur in order to increase the operation life of SOFC components. This report discusses the development of two such sensors, one based on thick film approach for sulfur monitoring and the second galvanic based for hydrocarbon monitoring.

  15. 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, ...

  16. Correlation between hydrocarbon distribution and water-hydrocarbon ratio in Fischer-Tropsch synthesis

    Institute of Scientific and Technical Information of China (English)

    Xiaofeng Zhou; Qingling Chen; Yuewu Tao; Huixin Weng

    2011-01-01

    In order to shorten the evaluation cycle of cobalt catalyst before the optimized catalyst is fixed on,a mathematical method is proposed to calculate weight percentage of C5+ hydrocarbons.Based on the carbide polymerization mechanism and the main hydrocarbons being linear alkanes and α-olefins,the correlation between hydrocarbon distribution and the molecular mass ratio of water to hydrocarbons is discussed.The result shows the ratio was within the range of 1.125-1.286 and the lower the ratio,the more gaseous hydrocarbons were obtained.Moreover,a linear equation between the weight percentage of C5+ hydrocarbons and the weight ratio of C5+ hydrocarbons to the total water is established.These results are validated by corresponding experiments.The weight percentage of C5+ hydrocarbons could be immediately calculated by this linear equation without detailed gas chromatography (GC) analysis of them.

  17. Poster 4: Investigating the first steps of hydrocarbon condensation in the laboratory and in Titan's atmosphere

    Science.gov (United States)

    Biennier, Ludovic; Bourgalais, Jeremy; Benidar, Abdessamad; Le Picard, Sebastien

    2016-06-01

    Hydrocarbons formed in Titan's cold atmosphere, starting with ethane C2H6, ethylene C2H4, acetylene C2H2, propane C3H8,... up to benzene C6H6, play some role in aerosol production, cloud processes, rain generation and Titan's lakes formation. We have started to study in the laboratory the kinetics of the first steps of condensation of these hydrocarbons. Rate coefficients are very sensitive to the description of the potential interaction surfaces of the molecules involved. Combined theoretical and experimental studies at the molecular level of the homogenous nucleation of various small molecules should improve greatly our fundamental understanding. This knowledge will serve as a model for studying more complex nucleation processes actually taking places in planetary atmospheres. Here we present the first experimental kinetic study of the dimerization of two small hydrocarbons: ethane C2H6 and propane C3H8. We have performed experiments to identify the temperature and partial densities ranges over which small hydrocarbon clusters form in saturated uniform supersonic flows. Using our unique reactor based on a Laval nozzle expansions, the kinetics of the formation has also been investigated down to 23 K. The chemical species present in the reactor are probed by a time of flight mass spectrometer equipped with an electron gun for soft ionization of the neutral reagents and products. This work aims at putting some constraints on the role of small hydrocarbon condensation in the formation of haze particles in the dense atmosphere of Titan.

  18. 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 ...

  19. 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...

  20. Process for the conversion of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Goudriaan, F.; Klinken, J.V.

    1978-11-21

    Residual hydrocarbon stocks obtained after vacuum distillation are converted into light distillates by certain sequences of processing steps including vacuum distillation, deasphalting, hydrocracking, atmospheric distillation and catalytic hydrotreating.

  1. 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)

  2. 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)

  3. Oligomerization of Glycine and Alanine Catalyzed by Iron Oxides: Implications for Prebiotic Chemistry

    Science.gov (United States)

    Shanker, Uma; Bhushan, Brij; Bhattacharjee, G.; Kamaluddin

    2012-02-01

    Iron oxide minerals are probable constituents of the sediments present in geothermal regions of the primitive earth. They might have adsorbed different organic monomers (amino acids, nucleotides etc.) and catalyzed polymerization processes leading to the formation of the first living cell. In the present work we tested the catalytic activity of three forms of iron oxides (Goethite, Akaganeite and Hematite) in the intermolecular condensation of each of the amino acids glycine and L-alanine. The effect of zinc oxide and titanium dioxide on the oligomerization has also been studied. Oligomerization studies were performed for 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The products formed were characterized by HPLC and ESI-MS techniques. All three forms of iron oxides catalyzed peptide bond formation (23.2% of gly2 and 10.65% of ala2). The reaction was monitored every 7 days. Formation of peptides was observed to start after 7 days at 50°C. Maximum yield of peptides was found after 35 days at 90°C. Reaction at 120°C favors formation of diketopiperazine derivatives. It is also important to note that after 35 days of reaction, goethite produced dimer and trimer with the highest yield among the oxides tested. We suggest that the activity of goethite could probably be due to its high surface area and surface acidity.

  4. 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.

  5. 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.

  6. 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...

  7. 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.

  8. Clay surface catalysis of formation of humic substances: potential role of maillard reactions

    Science.gov (United States)

    The mechanisms of the formation of humic substances are poorly understood, especially the condensation of amino acids and reducing sugars products (Maillard reaction) in soil environments. Clay minerals behave as Lewis and Brönsted acids and catalyze several reactions and likely to catalyze the Mai...

  9. 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

  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. Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

    DEFF Research Database (Denmark)

    Beier, Matthias Josef

    . Compared to alcohol oxidation the epoxidation of olefins with molecular oxygen is more difficult. Using N,N-dimethylformamide (DMF) as a solvent the Co-based metal-organic framework (MOF) STA-12(Co) catalyzed the epoxidation of styrene, (E)- and (Z)-stilbene. While the stilbene isomers were converted....... XAS revealed that silver was in the metallic state. Silver particle sizes estimated from XAS were significantly smaller (2- 3 nm) than from transmission electron microscopy (TEM) and X-ray diffraction (XRD; ca. 30 nm). It was proposed that silver-oxygen species might cause local disorder which would...... of silver was observed with the impregnated silver catalyst. By using silver supported on CeO2-SiO2 prepared by flame spray pyrolysis, leaching could be limited significantly. XAS investigation revealed that the active catalyst is most likely metallic silver. Compared to silver on silica calcined at 500 °C...

  13. Genesis and hydrocarbon significance of vesicular ignimbrite: A case study from Fengcheng Formation, Wu-Xia area, Junggar Basin, NW China%富孔熔结凝灰岩成因及油气意义——以准噶尔盆地乌—夏地区风城组为例

    Institute of Scientific and Technical Information of China (English)

    朱世发; 朱筱敏; 刘继山; 姚远; 鲜本忠; 牛花朋; 赵长永

    2012-01-01

    通过大量的岩心和薄片观察,分析准噶尔盆地乌—夏地区风城组熔结凝灰岩岩石学特征和孔隙发育特征,探讨富孔熔结凝灰岩成因和气孔发育机制.风城组沉积期火山作用以发育熔结火山碎屑岩为典型特征,岩石组分以塑性玻屑为主,棱角圆化,脱玻化特征明显;常见塑性浆屑变形揉皱、晶屑熔蚀现象.熔结凝灰岩中发育大量石泡,使熔结凝灰岩结构特征模糊.气孔是石泡构造的空腔,为冷凝收缩成因,受脱玻化作用影响挥发分或水蒸气散溢,形成的孔隙空间后期未被充填或少量充填.一个冷凝单元中石泡体发育在垂向上具有明显的分带特征:自下而上,气孔由少增多再减少.石泡孔洞的发育提高了熔结凝灰岩的储集能力,受熔结作用影响,石泡体未被压扁破坏.深埋、高孔熔结凝灰岩是重要的油气储集层,研究区高孔熔结凝灰岩具有良好的含油气性.图8表1参18%On the basis of a large number of cores and thin-sections observations, the petrologic and pore evolution characteristics of ignimbrite in the Fengcheng Formation in the Wu-Xia area, Junggar Basin, are studied, and the genesis of vesicular ignimbrite and formation mechanism of vesicles are analyzed. Volcanic action in the Fengcheng Formation is characterized by welded pyroclastic rocks. There are predominant plastic shards with rounded edges and obvious devitrification in the rocks. Plastic debris is deformed and wrinkled, and crystal fragments are usually corroded. A lot of lithophysae occur in the ignimbrite, and welded texture is obscured. Vesicles are the cavities of lithophysae, which are formed by solidification contraction. They have little or no late filling cement because the volatile constituent and water vapour in the bubbles have escaped with the help of devitrification. Lithophysae distribution within a cooling unit obviously has the characteristic of zonation in vertical: increasing upwards

  14. Amyloid-β and α-synuclein decrease the level of metal-catalyzed reactive oxygen species by radical scavenging and redox silencing

    DEFF Research Database (Denmark)

    Pedersen, Jeppe Trudslev; Chen, Serene W.; Borg, Christian Bernsen;

    2016-01-01

    The formation of reactive oxygen species (ROS) is linked to the pathogenesis of Alzheimer's and Parkinson's diseases. Here we have investigated the effect of soluble and aggregated Aβ and α-synuclein, associated with Alzheimer's and Parkinson's disease respectively, on the Cu2+-catalyzed formation......-active metal ions in the aggregates or as a downstream consequence of the formation of the patho-logical amyloid structures....

  15. 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.  ……

  16. Cell-surface acceleration of urokinase-catalyzed receptor cleavage

    DEFF Research Database (Denmark)

    Høyer-Hansen, G; Ploug, M; Behrendt, N;

    1997-01-01

    The urokinase-type plasminogen activator (uPA) binds to a specific cell-surface receptor, uPAR. On several cell types uPAR is present both in the full-length form and a cleaved form, uPAR(2+3), which is devoid of binding activity. The formation of uPAR(2+3) on cultured U937 cells is either directly...... by a prior incubation of the cells with uPA inactivated by diisopropyl fluorophosphate, demonstrating a requirement for specific receptor binding of the active uPA to obtain the high-efficiency cleavage of cell-bound uPAR. Furthermore, amino-terminal sequence analysis revealed that uPAR(2+3), purified from U......937 cell lysates, had the same amino termini as uPAR(2+3), generated by uPA in a purified system. In both cases cleavage had occurred at two positions in the hinge region connecting domain 1 and 2, between Arg83-Ala84 and Arg89-Ser90, respectively. The uPA-catalyzed cleavage of uPAR is a new negative...

  17. 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.

  18. Enzyme-Catalyzed Regioselective Modification of Starch Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Soma [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Sahoo, Bishwabhusan [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Teraoka, Iwao [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering; Miller, Lisa M. [Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source (NSLS); Gross, Richard A. [Polytechnic Univ., Brooklyn, NY (United States). National Science Foundation (NSF) Center for Biocatalysis and Bioprocessing of Macromolecules, Othmer Dept. of Chemical and Biological Science and Engineering

    2004-12-13

    The selective esterification of starch nanoparticles was performed using as catalyst Candida antartica Lipase B (CAL-B) in its immobilized (Novozym 435) and free (SP-525) forms. The starch nanoparticles were made accessible for acylation reactions by formation of Aerosol-OT (AOT, bis(2-ethylhexyl)sodium sulfosuccinate) stabilized microemulsions. Starch nanoparticles in microemulsions were reacted with vinyl stearate, ε-caprolactone, and maleic anhydride at 40 °C for 48 h to give starch esters with degrees of substitution (DS) of 0.8, 0.6, and 0.4, respectively. Substitution occurred regioselectively at the C-6 position of the glucose repeat units. Infrared microspectroscopy (IRMS) revealed that AOT-coated starch nanoparticles diffuse into the outer 50 μm shell of catalyst beads. Thus, even though CAL-B is immobilized within a macroporous resin, CAL-B is sufficiently accessible to the starch nanoparticles. When free CAL-B was incorporated along with starch within AOT-coated reversed micelles, CAL-B was also active and catalyzed the acylation with vinyl stearate (24 h, 40 °C) to give DS = 0.5. After removal of surfactant from the modified starch nanoparticles, they were dispersed in DMSO or water and were shown to retain their nanodimensions.

  19. 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

  20. Sedimentary charateristics and hydrocarbon accumulation in Northeast Sichuan basin

    Institute of Scientific and Technical Information of China (English)

    Jianming LI; Xiling WU; Rufeng LI; Liangjie TANG; Lei LI

    2008-01-01

    Northeast Sichuan basin is a Mesozoic-Cenozoic basin in the northern margin of the Yangtze plate which has a complex tectonic background and hydrocarbon accumulation history.By means of the analysis method of wave processes,major cycles of sedimentary wave process in this basin have been studied.The results show that there are five-order cycles corresponding to 760,220,100,35 and 20 Ma respectively,two first-order sedimentary cycles (220 Ma) and four secondorder sedimentary cycles (100 Ma).The authors find that the second-order sedimentary cycles are well matched with reservoir formation cycles through studying the relationship between second-order sedimentary cycles and reservoir formation cycles,and divide three reservoir formation cycles in this basin.

  1. Unsaturated medium hydrocarbons pollution evaluation

    International Nuclear Information System (INIS)

    When the so called porous unsaturated medium, that's the vertical subsoil section between both the ground and water-table level, is interested by a hydrocarbons spill, the problem to evaluate the pollution becomes difficult: considering, essentially, the natural coexistence in it of two fluids, air and water, and the interactions between them. This paper reports that the problems tend to increase when a third fluid, the pollutant, immiscible with water, is introduced into the medium: a three-phases flow, which presents several analogies with the flow conditions present in an oil-reservoir, will be established. In such a situation, it would be very useful to handle the matter by the commonly used parameters in the oil reservoirs studies such as: residual saturation, relative permeability, phases mobility, to derive a first semiquantitative estimation of the pollution. The subsoil pollution form hydrocarbons agents is one of the worldwide more diffused causes of contamination: such events are generally referable to two main effects: accidental (oil pipeline breakdowns, e.g.), and continuous (underground tanks breaks, industrial plants leakages, e.g.)

  2. Spring Coulee, Alberta : geology, production and potential hydrocarbon bearing zones

    Energy Technology Data Exchange (ETDEWEB)

    Ostridge, L.A.; Stewart, R.R. [Calgary Univ., AB (Canada). Dept. of Geoscience, Consortium for Research in Elastic Wave Exploration Seismology

    2008-07-01

    The mineral rights to 2 sections of land in the Spring Coulee area in southern Alberta are owned by the University of Calgary. Although the area is relatively unexplored, various pools in the area surrounding the University of Calgary's sections indicate that there is a potential for hydrocarbons to be located on the two sections. In order to examine the hydrocarbon potential on the two sections, the Consortium for Research in Elastic Wave Exploration Seismology (CREWES) Project shot an extensive 3C-2D seismic survey in January 2008. Gravity surveys across southern Alberta have observed anomalies and deep seismic data has indicated that Precambrian faulting is present on a large scale, which is then reflected in the younger Cretaceous sediments. This paper reported on a preliminary investigation into how the large-scale faulting occurs in the Spring Coulee area with respect to the University of Calgary land. The potential hydrocarbon bearing zones in the Spring Coulee area are the Bow Island, Base of Fish Scale, Sawtooth, Sunburst, Madison and Livingstone formations. Future work in the Spring Coulee area involves processing and interpreting the recently acquired seismic data, comparing large-scale basement faulting systems to seismic data and performing petrophysical and fluid replacement analyses of the area. 1 ref., 4 figs.

  3. Factors and features of the hydrocarbon status of soils

    Science.gov (United States)

    Gennadiev, A. N.; Pikovskii, Yu. I.; Zhidkin, A. P.; Kovach, R. G.; Koshovskii, T. S.; Smirnova, M. A.; Khlynina, N. I.; Tsibart, A. S.

    2015-11-01

    The hydrocarbon status (HCS) of soils has been characterized using a set of quantitative parameters, which can be obtained in the routine laboratory studies of soil samples. This is a general quantitative and qualitative characterization of hexane bitumoids and individual polycyclic aromatic hydrocarbons prevailing in natural objects. Field survey of soil air has been performed in order to determine the composition and content of gaseous hydrocarbons. The features and factors of soil HCS formation have been studied in soils of eight key sites in forest, steppe, and dry-steppe landscapes of European Russia. Along with zonal diversity, the presence of any local anomalous natural or technogenic factor capable of affecting the soil HCS (gas emanations from the deep lithosphere, specific parent rocks, pollutant fallout from the atmosphere, confinement to an oil field, etc.) has been used as the criterion of their selection. It has been shown that, just as the humus and salt statuses of soils have become their important integrated characteristics, so the study of soil HCS allows reaching a new level of knowledge of the nature of soils and their processes. The parameters of soil HCS adequately reflect the features of bioclimatic and topolithological factors of pedogenesis, the properties of soils, and the level of technogenic impact on the soil cover. Accumulation of new factual data and refinement of soil-geographical studies are necessary for more thorough study of soil HCS.

  4. Transformations and Tautomeric Equilibrium among Different Intermediates in Proline-Catalyzed Reactions of Aldehydes or Ketones

    Institute of Scientific and Technical Information of China (English)

    Li-hua Gan; Qing Chang; Jin Zhou

    2013-01-01

    The enamines,iminium ions,and oxazolidinones are thought to be the key intermediates in the proline-catalyzed reactions of aldehydes or ketones,but there is an extensive controversy about their roles.Here,the corresponding transition states connecting any two of the three kinds of species are located at the ωB97XD/6-311++G** level of theory.The calculations demonstrate that the oxazolidinones are the predominant species in both the gas phase and solvents; there exists tautomeric equilibrium among these species and the equilibriums are controlled by the employed solvents and temperature in the reaction.These results demonstrate that the concentration and role of the mentioned species are controlled by the employed solvent and temperature.A new reaction pathway is presented herein for the transformation between iminium ions and oxazolidinones through iminium ion-water complex and oxazolidinone-water complex.The calculations demonstrate that the rate-limiting step in proline-catalyzed Mannich reaction between acetaldehyde/keteones and N-Boc imines is the formation of the C-C bond rather than the intermediates tautomerization.These calculations rationalize the available experimental observations and can be valuable in optimizing the experimental conditions of asymmetric organic-catalyzed reactions of aldehydes or ketones.

  5. Biorefining: heterogeneously catalyzed reactions of carbohydrates for the production of furfural and hydroxymethylfurfural.

    Science.gov (United States)

    Karinen, Reetta; Vilonen, Kati; Niemelä, Marita

    2011-08-22

    Furfurals are important intermediates in the chemical industry. They are typically produced by homogeneous catalysis in aqueous solutions. However, heterogeneously catalyzed processes would be beneficial in view of the principles of green chemistry: the elimination of homogeneous mineral acids makes the reaction mixtures less corrosive, produces less waste, and facilitates easy separation and recovery of the catalyst. Finding an active and stable water-tolerant solid acid catalyst still poses a challenge for the production of furfural (furan-2-carbaldehyde) and 5-(hydroxymethyl)-2-furaldehyde (HMF). Furfural is produced in the dehydration of xylose, and HMF is formed from glucose and fructose in the presence of an acidic catalyst. Bases are not active in dehydration reaction but do catalyze the isomerization of monosaccharides, which is favorable when using glucose as a raw material. In addition to the desired dehydration of monosaccharides, many undesired side reactions take place, reducing the selectivity and deactivating the catalyst. In addition, the catalyst properties play an important role in the selectivity. In this Review, catalytic conversion approaches are summarized, focusing on the heterogeneously catalyzed formation of furfural. The attractiveness of catalytic concepts is evaluated, keeping in mind productivity, sustainability, and environmental footprint. PMID:21728248

  6. Characterisation of coking activity during supercritical hydrocarbon pyrolysis

    OpenAIRE

    Gascoin, Nicolas; Gillard, Philippe; Bouchez, Marc

    2008-01-01

    cited By (since 1996) 5 International audience The active cooling of the Supersonic Combustion Ramjet engine, for hypersonic flight purpose, is ensured thanks to fuel, n-dodecane for the present study. The endothermic fuel pyrolysis, starting above 800 K, could generate an unwanted coke formation. Experimental tests up to 1125 K and between 1 MPa and 6 MPa have been performed on the hydrocarbon fuel pyrolysis to evaluate the coking activity. 316L stainless steel, low carbon steel an...

  7. Evaluation of hydrocarbon potential, Task 8

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-09-30

    Task 8 is responsible for assessing the hydrocarbon potential of the Yucca Mountain vicinity. Our main focus is source rock stratigraphy in the Nevada Test Site (NTS) area in southern Nevada. In order to reconstruct the Paleozoic stratigraphy, we are also studying the geometry and kinematics of deformation at NTS. A thorough understanding of the structure will also be essential 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 are now provisionally limiting the name {open_quotes}Eleana Formation{close_quotes} to the rocks that make up the Eleana Range - i.e., the rocks that we have been calling {open_quotes}western Eleana{close_quotes}. The mudstone section (which we have until now called {open_quotes}eastern Eleana{close_quotes}) we are provisionally calling the {open_quotes}Chainman Shale{close_quotes}, in keeping with regional lithostratigraphic nomenclature. We continue to work out the internal stratigraphies and basin histories of both units; XRD (r-ray diffraction) determinations of clay mineralogy are an addition to our understanding of the Chainman. The basin histories place important constraints on regional paleogeographic and tectonic reconstructions. This year we have hired a consulting petroleum geologist for two jobs: (1) to review drillhole data from southern Nevada on file at NBMG and make recommendations about more detailed study of any interesting drillholes; and (2) to log the UE17e core (in the Chainman) and evaluate source rock potential. The results of these studies have been incorporated into this report, and the consultant`s reports.

  8. Crossed beam reaction of cyano radicals with hydrocarbon molecules. I. Chemical dynamics of cyanobenzene (C6H5CN; X 1A1) and perdeutero cyanobenzene (C6D5CN; X 1A1) formation from reaction of CN(X 2Σ+) with benzene C6H6(X 1A1g), and d6-benzene C6D6(X 1A1g)

    Science.gov (United States)

    Balucani, N.; Asvany, O.; Chang, A. H. H.; Lin, S. H.; Lee, Y. T.; Kaiser, R. I.; Bettinger, H. F.; Schleyer, P. v. R.; Schaefer, H. F.

    1999-10-01

    rich planets and satellites such as Saturn's moon Titan. This reaction might further present a barrierless route to the formation of heteropolycyclic aromatic hydrocarbons via cyanobenzene in these extraterrestrial environments as well as hydrocarbon rich flames.

  9. Fundamentals of heterogeneously catalyzed reactions of environmental importance

    Science.gov (United States)

    Deshmukh, Subodh Shrinivas

    Reaction kinetics and spectroscopic characterization are valuable tools for understanding heterogeneously catalyzed chemical reactions. The objective of this work was to apply the tools of catalysis and reaction kinetics to understand the fundamentals of chemical surface phenomena for environmentally important reactions. This thesis presents our work in two areas of catalytic reactions for pollution abatement---"chlorofluorocarbon (CFC) treatment chemistry" and "sulfur-tolerant auto exhaust catalysts." The ozone depletion potential of CFCs has resulted in a great interest in the academic and industrial communities to find replacements for these chemicals. Hydrofluorocarbons (HFCs) are amongst the best "environmentally benign" candidates for CFC replacement. One selective pathway for the synthesis of HFCs is via the hydrodechlorination of CFCs. This route has the added benefit of destroying harmful CFC stockpiles and converting them into more useful chemicals. The work in Chapter 3 shows that parallel hydrogenation pathways starting from a common CF2 species can explain the formation of the products CH2F2 and CH4 for the hydrodechlorination of CF2Cl2 over Pd/AlF3. Transient kinetics experiments using C2H4 as a trapping agent for surface carbenes have provided evidence for the presence of CH2 species on the catalyst surface during this reaction. The absence of either coupling products or trapped products containing F suggests that the rate of hydrogenation of surface CF2 species is faster than that of surface CH2 species. Another important class of CFC reactions is oxide-catalyzed disproportionations to control the number and position of halogen atoms in the CFC/HFC molecule. Chapter 4 combines the use of reaction kinetics tools and spectroscopic characterization techniques to understand the adsorption and reaction of CF3CFCl 2 over gamma-Al2O3. The CF3CFCl 2 reaction over gamma-Al2O3 lead to a modification of the gamma-Al2O3 surface due to fluorination and the

  10. Pressure sensitive adhesive using light color, low softening point petroleum hydrocarbon resins

    Energy Technology Data Exchange (ETDEWEB)

    Ahner, M.E.

    1987-07-28

    This patent describes an adhesive composition comprising from about 20% to about 80% by weight of a copolymer and, correspondingly, from about 80% to about 20% by weight of a tackifying petroleum hydrocarbon resin having a softening point of from 0/sup 0/C to about 40/sup 0/C. It has a number average molecular weight of from about 100 to about 600, and a Gardner color less than about 7 prepared by the aluminum chloride catalyzed Friedel Crafts polymerization of a hydrocarbon feed comprising: (a) from about 5% to about 75% by weight of C/sub 8/ to C/sub 10/ vinyl aromatic hydrocarbon stream; (b) from about 10% to about 35% by weight of a piperylene concentrate; and (c) from about 25% to about 70% by weight of a C/sub 4/ to C/sub 8/ monoolefin chain transfer agent of the formula RR'C=CHR'' where R and R' are C/sub 1/ to C/sub 5/ alkyl, and R'' is H or C/sub 1/ to C/sub 4/ alkyl group.

  11. Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

    Science.gov (United States)

    Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

    2015-12-01

    The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

  12. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    Science.gov (United States)

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  13. Potential contributions of extremophiles to hydrocarbon resources in marine extreme environments:A review

    Institute of Scientific and Technical Information of China (English)

    WANG Jiasheng; WANG Yongbiao; LI Qing

    2007-01-01

    To understand the potential mechanism of marine extremophiles participating in the formation and the evolution of hydrocarbon resources in marine extreme environments,some typical kinds of extremophiles and their distributions in marine hydrothermal and cold vents are discussed and evaluated respectively.The potential relationship between extremophile activities and hydrocarbon resources in marine extreme environments are then discussed in details.It could be now preliminary concluded that archaea and bacteria are the two main kinds of extremophiles in marine extreme environments.The dominating microbe communities in hydrothermal vents are heterotrophic zymogens,sulfate reducers and methanogens,while the ANME-2 group(Methanosarcinales) surrounded by sulfate-reducing bacteria and ANME-1 group dominate in cold vents.Marine extremophiles would be able to use CH,and H2S to synthesize energy for metabolism and to support food chains for other unique macrobiota nearby,which together present a high abundance but a low diversity with distinct characteristics of horizontal and vertical distributions.Marine extremophiles might play an important role either directly or indirectly in the processes of hydrocarbon formation and subsequent alteration,and could indicate the evolution of hydrocarbon resources in marine extreme environments.Our research thus has a great significance both in theoretical approach of potential hydrocarbon resources formed by marine extremophile activities and in practical exploration of the potential hydrocarbonsource sedimentary layers formed in the Earth history or the potential strata in southern China.

  14. Dual-Bed Catalytic System for Direct Conversion of Methane to Liquid Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    N.A.S.Amin; Sriraj Ammasi

    2006-01-01

    A dual-bed catalytic system is proposed for the direct conversion of methane to liquid hydrocarbons. In this system, methane is converted in the first stage to oxidative coupling of methane (OCM) products by selective catalytic oxidation with oxygen over La-supported MgO catalyst. The second bed, comprising of the HZSM-5 zeolite catalyst, is used for the oligomerization of OCM light hydrocarbon products to liquid hydrocarbons. The effects of temperature (650-800 ℃), methane to oxygen ratio (4-10), and SiO2/Al2O3 ratio of the HZSM-5 zeolite catalyst on the process are studied. At higher reaction temperatures, there is considerable dealumination of HZSM-5, and thus its catalytic performance is reduced. The acidity of HZSM-5 in the second bed is responsible for the oligomerization reaction that leads to the formation of liquid hydrocarbons. The activities of the oligomerization sites were unequivocally affected by the SiO2/Al2O3 ratio. The relation between the acidity and the activity of HZSM-5 is studied by means of TPD-NH3 techniques. The rise in oxygen concentration is not beneficial for the C5+ selectivity, where the combustion reaction of intermediate hydrocarbon products that leads to the formation of carbon oxide (CO+CO2) products is more dominant than the oligomerization reaction. The dual-bed catalytic system is highly potential for directly converting methane to liquid fuels.

  15. Litho-seismic data handling for hydrocarbon reservoir estimate. Fuzzy system modelling approach

    Energy Technology Data Exchange (ETDEWEB)

    Shyllon, E.A.; Olaleye, J.B.; Olunloyo, V.O.S. [Geoinformatics Laboratory, Faculty of Engineering, University of Lagos, Lagos (Nigeria)

    2001-11-01

    Fuzzy system modelling provides a strict mathematical environment in which vague conceptual phenomena can be rigorously studied. For hydrocarbon reservoir, its data model consists of parameters such as location identifier, time as well as attributes such as porosity, saturation, hydrocarbon and formation volume factor. These are usually developed from the litho-seismic data of an oilfield. In particular, fuzzy descriptions are obtained for the main parameters that define the structure and model of the hydrocarbon formation. From these, the membership grade functions of the fuzzy subsets are determined using an interval [0,1]. To simplify the model formulation of the ill-defined problem of oilfield services, the results of core analysis are expressed with linguistic quantifiers such as minimum, maximum or most likely porosity, saturation hydrocarbon, etc. Our model provides a new approach for tackling the sustainable development and management of hydrocarbon reservoir on stream and enhanced recovery. In this example, the potential acreage is mapped and the reservoir estimate is obtained easily using defuzzifier such as mean of maxima.

  16. Ruthenium-Catalyzed Hydroalkynylative Cyclization of 1,6-Enynes Induced by Substituent Effects.

    Science.gov (United States)

    Liu, Rui; Ni, Zhenjie; Giordano, Laurent; Tenaglia, Alphonse

    2016-08-19

    The ruthenium-catalyzed 1,6-enyne cyclization in the presence of bulky substituted terminal alkyne proceeds smoothly at room temperature to afford highly substituted five-membered cyclic compounds featuring a 1,5-enyne motif. Deuterium-labeling experiments showed that the key ruthenacyclopentene intermediate undergoes cleavage of metal-carbon bonds through the metal-assisted σ-bond metathesis reaction, thus leading to the formation of C(sp(2))-H and C(sp(3))-C(sp) bonds. PMID:27504966

  17. Enzyme-catalyzed ring-opening polymerization of unsubstituted beta-lactam

    OpenAIRE

    Schwab, Leendert W.; Kroon, Renee; Schouten, Arend Jan; Loos, Katja

    2008-01-01

    The synthesis of poly(beta-alanine) by Candida antarctica lipase B immobilized as novozyme 435 catalyzed ring-opening of 2-azetidinone is reported. After removal of cyclic side products and low molecular weight species pure linear poly(beta-alanine) is obtained. The formation of the polymer is confirmed with (1)H NMR spectroscopy and MALDI-TOF mass spectrometry. The average degree of polymerization of the obtained polymer is limited to DP=8 by its solubility in the reaction medium. Control ex...

  18. Enzyme-Catalyzed Modifications of Polysaccharides and Poly(ethylene glycol

    Directory of Open Access Journals (Sweden)

    H. N. Cheng

    2012-06-01

    Full Text Available Polysaccharides are used extensively in various industrial applications, such as food, adhesives, coatings, construction, paper, pharmaceuticals, and personal care. Many polysaccharide structures need to be modified in order to improve their end-use properties; this is mostly done through chemical reactions. In the past 20 years many enzyme-catalyzed modifications have been developed to supplement chemical derivatization methods. Typical reactions include enzymatic oxidation, ester formation, amidation, glycosylation, and molecular weight reduction. These reactions are reviewed in this paper, with emphasis placed on the work done by the authors. The polymers covered in this review include cellulosic derivatives, starch, guar, pectin, and poly(ethylene glycol.

  19. Lochon Catalyzed D-D Fusion in Deuterated Palladium in the Solid State

    CERN Document Server

    Sinha, K P

    2008-01-01

    Lochons (local charged bosons or local electron pairs) can form on D+ to give D- (bosonic ions) in Palladium Deuteride in the solid state. Such entities will occur at special sites or in linear channel owing to strong electron-phonon interaction or due to potential inversion on metallic electrodes. These lochons can catalyze D- - D+ fusion as a consequence of internal conversion leading to the formation of He-4 plus production of energy (Q=23.8 MeV) which is carried by the alpha particle and the ejected electron-pair. The reaction rate for this fusion process is calculated.

  20. Palladium(II)-Catalyzed Tandem Synthesis of Acenes Using Carboxylic Acids as Traceless Directing Groups.

    Science.gov (United States)

    Kim, Kiho; Vasu, Dhananjayan; Im, Honggu; Hong, Sungwoo

    2016-07-18

    A straightforward synthetic strategy for generating useful anthracene derivatives was developed involving palladium(II)-catalyzed tandem transformation with carboxylic acids as traceless directing groups. Carboxyl-directed C-H alkenylation, carboxyl-directed secondary C-H activation and rollover, intramolecular C-C bond formation, and decarboxylative aromatization are proposed as the key steps in the tandem reaction pathway. This novel synthetic route utilizes a broad range of substrates and provides a convenient synthetic tool that allows access to acenes. PMID:27244536

  1. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Directory of Open Access Journals (Sweden)

    Cláudia M. B. Neves

    2012-01-01

    Full Text Available This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy.

  2. Copper-Catalyzed Enantioselective Synthesis of α-Hydroxyamine Using Monodentate Phosphoramidites

    Institute of Scientific and Technical Information of China (English)

    DONG,Lin; CUN,Lin-Feng; GONG,Liu-Zhu; MI,Ai-Qiao; JIANG,Yao-Zhong

    2004-01-01

    @@ Development of new methods for the introduction of a nitrogen atom to a carbonyl group is still the most important synthetic target. Cu-catalyzed addition of organozinc reagents to α,β-unsaturated carbonyl compounds has been the subject of intensive investigation.[1] Moreover, trapping of the intermediate Zn-enolates has been achieved using nitrosobenzene. To demonstrate the feasibility of developing enantioselective variants of these tandem C-C bond formations,α,β-unsaturated substrates a~d was subjected to standard reaction conditions using Feringa's (L1*, L2*) and our own phosphoramidite ligands (L3*, L4*). In this reaction, medium to high levels of enantioselectivities were observed.

  3. Lewis Acid Catalyzed Selective Reactions of Donor-Acceptor Cyclopropanes with 2-Naphthols.

    Science.gov (United States)

    Kaicharla, Trinadh; Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G; Biju, Akkattu T

    2016-08-16

    Lewis acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with 2-naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)3 as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene-fused cyclopentanes. Interestingly, engaging Sc(OTf)3 as the Lewis acid, a Friedel-Crafts-type addition of 2-naphthols to cyclopropanes takes place, thus affording functionalized 2-naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields. PMID:27391792

  4. [Development of novel methods for synthesis of heterocyclic compounds catalyzed by transition metals in fluorinated alcohols].

    Science.gov (United States)

    Saito, Akio

    2008-08-01

    New possibilities for catalytic syntheses of lactone derivatives and nitrogen-containing heterocyclic compounds in fluorinated alcohols are described. The cationic Rh(I) catalyst in fluorinated alcohol solvents (hexafluoroisopropanol: HFIP, trifluoroethanol: TFE) brought about not only mild cycloaddition reactions of ester-tethered compounds but also a facile formation of indole derivatives by the aromatic amino-Claisen rearrangement of N-propargyl aniline derivatives. The use of HFIP as an additive exerted a remarkable effect on the Pictet-Spengler reaction catalyzed by the fluorinated surfactant-combined Brønsted acid catalyst in water.

  5. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Neves, Claudia M.B.; Simoes, Mario M.Q.; Domingues, Fernando M.J.; Neves, M. Graca P.M.S.; Cavaleiro, Jose A.S., E-mail: msimoes@ua.pt [Dept. de Quimica, QOPNA, Universidade de Aveiro (Portugal)

    2012-07-01

    This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H{sub 2}O{sub 2}, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy. (author)

  6. Te-doping of self-catalyzed GaAs nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Suomalainen, S., E-mail: soile.suomalainen@tut.fi; Hakkarainen, T. V.; Salminen, T.; Koskinen, R.; Guina, Mircea [Optoelectronics Research Centre, Tampere University of Technology, FI-33101 Tampere (Finland); Honkanen, M. [Department of Material Science, Tampere University of Technology, FI-33101 Tampere (Finland); Luna, E. [Paul-Drude-Institut für Festkörperelektronik, Hausvogteiplatz 5-7, 10117 Berlin (Germany)

    2015-07-06

    Tellurium (Te)-doping of self-catalyzed GaAs nanowires (NWs) grown by molecular beam epitaxy is reported. The effect of Te-doping on the morphological and crystal structure of the NWs is investigated by scanning electron microscopy and high-resolution transmission electron microscopy. The study reveals that the lateral growth rate increases and axial growth rate decreases with increasing Te doping level. The changes in the NW morphology can be reverted to some extent by changing the growth temperature. At high doping levels, formation of twinning superlattice is observed alongside with the (111)-facetted sidewalls. Finally, the incorporation of Te is confirmed by Raman spectroscopy.

  7. Catalyzed oxidation of 2,6-dimethylphenol in Triton X-100 micellar solution

    Institute of Scientific and Technical Information of China (English)

    Jie Zhu; Xiang Guang Meng; Hai Dong Wang; Shan Dong Liu; Qin Hui Pang; Juan Du; Xian Cheng Zeng

    2007-01-01

    The oxidative coupling reaction of 2,6-dimethylphenol with H2O2 catalyzed by a copper(Ⅱ) Schiff complex in aqueous and Triton X-100 micellar solution under mild conditions was investigated. The kinetics of formation of 3,3',5,5'-tetramethyl-4,4'-diphenoquinone (DPQ) was studied. Rate constant k2 were obtained. The optimum pH for DPQ generation reaction is 7.25. The main product was DPQ in aqueous buffer solution, but PPE and the oxidized products of PPE remained in Triton X-100 micellar solution.

  8. Formation of H2 and CH4 by weathering of olivine at temperatures between 30 and 70°C

    Directory of Open Access Journals (Sweden)

    Crill Patrick

    2011-06-01

    Full Text Available Abstract Hydrocarbons such as CH4 are known to be formed through the Fischer-Tropsch or Sabatier type reactions in hydrothermal systems usually at temperatures above 100°C. Weathering of olivine is sometimes suggested to account for abiotic formation of CH4 through its redox lowering and water splitting properties. Knowledge about the CH4 and H2 formation processes at low temperatures is important for the research about the origin and cause of early Earth and Martian CH4 and for CO2 sequestration. We have conducted a series of low temperature, long-term weathering experiments in which we have tested the CH4 and H2 formation potential of forsteritic olivine. The results show low temperature CH4 production that is probably influenced by chromite and magnetite as catalysts. Extensive analyses of a potential CH4 source trapped in the crystal structure of the olivine showed no signs of incorporated CH4. Also, the available sources of organic carbon were not enough to support the total amount of CH4 detected in our experiments. There was also a linear relationship between silica release into solution and the net CH4 accumulation into the incubation bottle headspaces suggesting that CH4 formation under these conditions could be a qualitative indicator of olivine dissolution. It is likely that minerals such as magnetite, chromite and other metal-rich minerals found on the olivine surface catalyze the formation of CH4, because of the low temperature of the system. This may expand the range of environments plausible for abiotic CH4 formation both on Earth and on other terrestrial bodies.

  9. Polycyclic aromatic hydrocarbons with SPICA

    CERN Document Server

    Berne, O; Mulas, G; Tielens, A G G M; Goicoechea, J R

    2009-01-01

    Thanks to high sensitivity and angular resolution and broad spectral coverage, SPICA will offer a unique opportunity to better characterize the nature of polycyclic aromatic hydrocarbons (PAHs) and very small grains (VSGs), to better use them as probes of astrophysical environments. The angular resolution will enable to probe the chemical frontiers in the evolution process from VSGs to neutral PAHs, to ionized PAHs and to "Grand-PAHs" in photodissotiation regions and HII regions, as a function of G$_0$/n (UV radiation field / density). High sensitivity will favor the detection of the far-IR skeletal emission bands of PAHs, which provide specific fingerprints and could lead to the identification of individual PAHs. This overall characterization will allow to use PAH and VSG populations as tracers of physical conditions in spatially resolved protoplanetary disks and nearby galaxies (using mid-IR instruments), and in high redshift galaxies (using the far-IR instrument), thanks to the broad spectral coverage SPIC...

  10. High Molecular Weight Petrogenic and Pyrogenic Hydrocarbons in Aquatic Environments

    Science.gov (United States)

    Abrajano, T. A., Jr.; Yan, B.; O'Malley, V.

    2003-12-01

    compounds were introduced to shallow environments through forest fires and natural coking of crude oil ( Ballentine et al., 1996; O'Malley et al., 1997). The full development of natural microbial enzymatic systems that can utilize HMW hydrocarbons as carbon or energy source attests to the antiquity of hydrocarbon dispersal processes in the environment. The environmental concern is, therefore, primarily due to the rate and spatial scale by which petroleum products are released in modern times, particularly with respect to the environmental sensitivity of some ecosystems to these releases ( Schwarzenbach et al., 1993; Eganhouse, 1997; NRC, 2002).Crude oil is produced by diagenetic and thermal maturation of terrestrial and marine plant and animal materials in source rocks and petroleum reservoirs. Most of the petroleum in use today is produced by thermal and bacterial decomposition of phytoplankton material that once lived near the surface of the world's ocean, lake, and river waters (Tissot and Welte, 1984). Terrestrially derived organic matter can be regionally significant, and is the second major contributor to the worldwide oil inventory ( Tissot and Welte, 1984; Peters and Moldowan, 1993; Engel and Macko, 1993). The existing theories hold that the organic matter present in crude oil consists of unconverted original biopolymers and new compounds polymerized by reactions promoted by time and increasing temperature in deep geologic formations. The resulting oil can migrate from source to reservoir rocks where the new geochemical conditions may again lead to further transformation of the petrogenic compounds. Any subsequent changes in reservoir conditions brought about by uplift, interaction with aqueous fluids, or even direct human intervention (e.g., drilling, water washing) likewise could alter the geochemical makeup of the petrogenic compounds. Much of our understanding of environmental sources and fate of hydrocarbon compounds in shallow environments indeed borrowed from

  11. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

    International Nuclear Information System (INIS)

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. 29Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. - Graphical abstract: The morphologies and microstructures of acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were observed by scanning electron microscope and transmission electron microscope. MBGMs-A exhibits a dense structure and a porous can be observed in MBGMs-B. The microspheres have a quick inducing-apatite formation ability and show a sustained release of alendronate (AL). Highlights: • A rapid method was reported to prepare mesoporous bioactive glass microspheres. • The addition of ammonia significantly shortens the preparation time. • Acid and acid-alkali co-catalyzed microspheres were studied for the first time. • The materials exhibited excellent in vitro bioactivity and drug

  12. Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones.

    Science.gov (United States)

    Zhuo, Lian-Gang; Yao, Zhong-Ke; Yu, Zhi-Xiang

    2013-09-20

    Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.

  13. Mechanisms of bacterially catalyzed reductive dehalogenation

    Energy Technology Data Exchange (ETDEWEB)

    Picardal, F.W.

    1992-12-31

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using {sup 14}C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  14. Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Molten, P.M.; Miller, R.K.; Donovan, J.M.; Demmitt, T.F.

    1977-01-01

    The overall mechanism of cellulose converson in hot aqueous alkali appears to be one of degradation through glucose to low molecular weight saccharinic acids, dihydroxybutyric acid, glycolic acid, and carbonyl products such as acetone, acetaldehyde, formaldehyde, and similar compounds. Although the products identified in the present report were fairly complex furans, carbocyclic ketones, unsaturated hydrocarbons, and aromatic compounds, nevertheless, in most cases, they could have been formed from simple carbonyl compounds through a series of condensations involving carbanion intermediates. It is conceivable that residual alkali in the oil during acetone extraction could have given rise to diacetone alcohol as an artifact. This is refuted by examination of an aqueous residue which was extracted with diethyl ether and which was never exposed to any acetone: Compounds derived from diacetone alcohol (such as mesityl oxide or 4-methyl-3-penten-2-one) were also identified in the diethyl ether extract of the aqueous phase. Other compounds were identified in the oil acetone extract which could not have been derived from acetone or diacetone alcohol, but which could have been formed from other carbonyl compounds by the same mechanism. Hence, diacetone alcohol is a genuine product of cellulose conversion although apparently not an intermediate in further synthesis of other products. The further reaction of the postulated cyclic intermediates, and the route to formation of unsaturated hydrocarbons of high molecular weight is intended to be the next subject of investigation in the current work. The fundamental difference in the mechanism of cellulose conversion to oil by pyrolysis and by aqueous alkaline digestion predicted by theory is therefore confirmed. Pyrolysis products may be explained generally by carbonium ion and free radical reactions (in fact, cellulose decomposition is acid-catalyzed), while in aqueous alkali, nucleophilic carbanion reactions are favored.

  15. Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2-Arylbenzoxazoles%Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2-Arylbenzoxazoles

    Institute of Scientific and Technical Information of China (English)

    冷瑜婷; 杨帆; 吴养洁; 李克

    2011-01-01

    An efficient and facile protocol for palladacycle-catalyzed chlorination of 2-arylbenzoxazoles was developed. The results represent the first examples involving the palladacycle as the catalyst for such chlorination. This chlori- nation was not a ligand-directed ortho-C--H activation, but an electrophilic substitution process at the para-position of the nitrogen atom in the benzo ring of benzoxazole moiety, the regiochemistry of which had been confirmed by HMBC spectral analysis. The catalytic system could tolerate various halogen atoms, such as F, Cl and Br, affording the corresponding products in moderate to excellent yields.

  16. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  17. Functioned Calix[4]arenes as Artificial Enzymes Catalyze Aldol Condensation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Aldolase models derived from calix[4]arene were designed and synthesized. The aldol condensation of p-nitrobenzaldehyde with acetone was catalyzed by the synthetic enzymes proceeded under mild conditions to offer chiefly aldol-type product in good yield.

  18. Amino Acids Catalyzed Direct Aldol Reactions in Aqueous Micelles

    Institute of Scientific and Technical Information of China (English)

    PENG Yi-Yuan; WANG Qi; DING Qiu-Ping; HE Jia-Qi; CHENG Jin-Pei

    2003-01-01

    @@ Since the discovery of its roles as a good small-organic-molecule catalyst in intramolecular aldol reactions, pro line has drawn considerable attention in synthetic chemistry due to its similarity to the type-Ⅰ aldolases. Recently,List and others have reported some new direct asymmetric intermolecular reactions catalyzed by proline, including aldol, Mannich, Michael, and other analogous reactions. Except for two recent examples, [1,2] proline catalyzed aldol reactions in aqueous micelles have not been reported, nor have other amino acids as organocatalysts in directly catalyzing aldol reaction been reported. Herein we wish to present our recent results regarding environmentally be nign direct aldol reactions catalyzed by amino acids including proline, histidine and arginine in aqueous media.

  19. Lipase catalyzed synthesis of epoxy-fatty acids

    Institute of Scientific and Technical Information of China (English)

    CHEN, Qian; LI, Zu-Yi

    2000-01-01

    Lipase catalyzed synthesis of epoxy-fatty acidas from unsaturated carboxylic acids was investigated.Under mild conditions unsaturated arboxylic acids were convcveed to peroxide,then the unsaturated peroxycarboxylic acids epoxidised the C=C bond of themselves

  20. The nonoxidative conversion of nitroethane to ethylnitronate in Neurospora crassa 2-nitropropane dioxygenase is catalyzed by histidine 196.

    Science.gov (United States)

    Francis, Kevin; Gadda, Giovanni

    2008-09-01

    The deprotonation of nitroethane catalyzed by Neurospora crassa 2-nitropropane dioxygenase was investigated by measuring the formation and release of ethylnitronate formed in turnover as a function of pH and through mutagenesis studies. Progress curves for the enzymatic reaction obtained by following the increase in absorbance at 228 nm over time were visibly nonlinear, requiring a logarithmic approximation of the initial reaction rates for the determination of the kinetic parameters of the enzyme. The pH dependence of the second-order rate constant k cat/ K m with nitroethane as substrate implicates the presence of a group with a p K a of 8.1 +/- 0.1 that must be unprotonated for nitronate formation. Mutagenesis studies suggest that this group is histidine 196 as evident from the inability of a H196N variant form of the enzyme to catalyze the formation of ethylnitronate from nitroethane. Replacement of histidine 196 with asparagine resulted in an approximately 15-fold increase in the k cat/ K m with ethylnitronate as compared to the wild-type, which results from the inability of the mutant enzyme to undergo nonoxidative turnover. The results presented herein are consistent with a branched catalytic mechanism for the enzyme in which the ethylnitronate intermediate formed from the H196-catalyzed deprotonation of nitroethane partitions between release from the active site and oxidative denitrification to yield acetaldehyde and nitrite. PMID:18690716