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

International Nuclear Information System (INIS)

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

2012-01-01

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

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

Science.gov (United States)

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

2012-02-01

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

Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

Science.gov (United States)

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

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

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

International Nuclear Information System (INIS)

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

2001-05-01

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

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

DEFF Research Database (Denmark)

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

1993-01-01

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

Optrode for sensing hydrocarbons

Science.gov (United States)

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

1988-09-13

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2001-05-01

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

Halogen-Mediated Conversion of Hydrocarbons to Commodities.

Science.gov (United States)

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

2017-03-08

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

Hydrocarbons and air pollution

International Nuclear Information System (INIS)

Herz, O.

1992-01-01

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

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

International Nuclear Information System (INIS)

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

1992-01-01

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

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

NARCIS (Netherlands)

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

1994-01-01

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

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

Directory of Open Access Journals (Sweden)

Gerardo Carlos Torres

2012-01-01

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

The photochemical reaction of hydrocarbons under extreme thermobaric conditions

Science.gov (United States)

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

2017-10-01

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

Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

Energy Technology Data Exchange (ETDEWEB)

Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)

1997-04-01

The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

Steam hydrocarbon cracking and reforming

NARCIS (Netherlands)

Golombok, M.

2004-01-01

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

Production of light hydrocarbons, etc. [from heavy hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1937-10-07

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

Cortical involvement in anticipatory postural reactions in man

DEFF Research Database (Denmark)

Petersen, Tue Hvass; Rosenberg, Kasper; Petersen, Nicolas Caesar

2009-01-01

All movements are accompanied by postural reactions which ensure that the balance of the body is maintained. It has not been resolved that to what extent the primary motor cortex and corticospinal tract are involved in the control of these reactions. Here, we investigated the contribution...... of the corticospinal tract to the activation of the soleus (SOL) muscle in standing human subjects (n = 10) in relation to voluntary heel raise, anticipatory postural activation of the soleus muscle when the subject pulled a handle and to reflex activation of the soleus muscle when the subject was suddenly pulled...... was observed prior to EMG onset for the external perturbation. These data suggest that the primary motor cortex is involved in activating the SOL muscle as part of an anticipatory postural reaction....

Process for conversion of lignin to reformulated hydrocarbon gasoline

Science.gov (United States)

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

1999-09-28

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

Purifying hydrocarbon oils

Energy Technology Data Exchange (ETDEWEB)

Rostin, H

1938-08-11

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

Study of higher hydrocarbon production during ethylacetylene pyrolysis using laser-generated vacuum-ultraviolet photoionization detection

Energy Technology Data Exchange (ETDEWEB)

Boyle, J.; Pfefferle, L. (Yale Univ., New Haven, CT (USA))

1990-04-19

Higher hydrocarbon formation during the pyrolysis of ethylacetylene in a microjet reactor was studied by vacuum-ultraviolet photoionization time-of-flight mass spectrometry. At the wavelength employed, this ionization technique allows for the simultaneous detection of both stable and intermediate polyatomic species with ionization potentials below 10.49 eV, including most hydrocarbons with two or more carbon atoms. Minimal fragmentation simplifies the determination of parent species and allows identification of probable reaction pathways involving hydrocarbon radicals as well as stable species. The pyrolysis of ethylacetylene was carried out in the fast-flow microjet reactor (residence times 1-2 ms) at temperatures from 300 to 1,600 K.

Production of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Day, D T; Day, R E

1920-04-27

A process is disclosed of converting hydro-carbon oils having high boiling points to hydro-carbon oils having low boiling points, which process comprises adding the oil to be treated to a mass of hydro-carbon oil bearing shale, passing the shale with the oil through a conveyor retort and subjecting the material while in the retort to a heat treatment involving a temperature of at least 500/sup 0/F.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-01

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

Reactions of BBr(n)(+) (n = 0--2) at fluorinated and hydrocarbon self-assembled monolayer surfaces: observations of chemical selectivity in ion--surface scattering.

Science.gov (United States)

Wade, N; Shen, J; Koskinen, J; Cooks, R G

2001-07-01

Ion-surface reactions involving BBr(n)(+) (n = 0--2) with a fluorinated self-assembled monolayer (F-SAM) surface were investigated using a multi-sector scattering mass spectrometer. Collisions of the B(+) ion yield BF(2)(+) at threshold energy with the simpler product ion BF(+)* appearing at higher collision energies and remaining of lower abundance than BF(2)(+) at all energies examined. In addition, the reactively sputtered ion CF(+) accompanies the formation of BF(2)(+) at low collision energies. These results stand in contrast with previous data on the ion-surface reactions of atomic ions with the F-SAM surface in that the threshold and most abundant reaction products in those cases involved the abstraction of a single fluorine atom. Gas-phase enthalpy data are consistent with BF(2)(+) being the thermodynamically favored product. The fact that the abundance of BF(2)(+) is relatively low and relatively insensitive to changes in collision energy suggests that this reaction proceeds through an entropically demanding intermediate at the vacuum--surface interface, one which involves interaction of the B(+) ion simultaneously with two fluorine atoms. By contrast with the reaction of B(+), the odd-electron species BBr(+)* reacts with the F-SAM surface to yield an abundant single-fluorine abstraction product, BBrF(+). Corresponding gas-phase ion--molecule experiments involving B(+) and BBr(+)* with C(6)F(14) also yield the products BF(+)* and BF(2)(+), but only in extremely low abundances and with no preference for double fluorine abstraction. Ion--surface reactions were also investigated for BBr(n)(+) (n = 0-2) with a hydrocarbon self-assembled monolayer (H-SAM) surface. Reaction of the B(+) ion and dissociative reactions of BBr(+)* result in the formation of BH(2)(+), while the thermodynamically less favorable product BH(+)* is not observed. Collisions of BBr(2)(+) with the H-SAM surface yield the dissociative ion-surface reaction products, BBrH(+) and BBrCH(3

Method for upgrading diene-containing hydrocarbon mixtures

Energy Technology Data Exchange (ETDEWEB)

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

1984-05-22

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

Effect of hydrocarbons on plasma treatment of NOx

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Laboratory approaches of nuclear reactions involved in primordial and stellar nucleosynthesis

International Nuclear Information System (INIS)

Rolfs, C.; California Inst. of Tech., Pasadena

1986-01-01

Laboratory-based studies of primordial and stellar nucleosynthesis are reviewed, with emphasis on the nuclear reactions induced by charged particles. The analytical approach used to investigate nuclear reactions associated with stellar reactions is described, as well as the experimental details and procedures used to investigate nuclear reactions induced by charged particles. The present knowledge of some of the key reactions involved in primordial nucleosynthesis is discussed, along with the progress and problems of nuclear reactions involved in the hydrogen and helium burning phases of a star. Finally, a description is given of new experimental techniques which might be useful for future experiments in the field of nuclear astrophysics. (U.K.)

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-07-01

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

Laboratory Studies of Hydrocarbon Oxidation Mechanisms

Science.gov (United States)

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

2001-12-01

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

Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions

Energy Technology Data Exchange (ETDEWEB)

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

2018-04-08

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

High Temperature Chemistry of Aromatic Hydrocarbons. Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Scott, Lawrence T. [Boston College, Chestnut Hill, MA (United States). Merkert Chemistry Center, Dept. of Chemistry

2017-05-15

The primary goal of this research was to uncover the principal reaction channels available to polycyclic aromatic hydrocarbons (PAHs) at high temperatures in the gas phase and to establish the factors that determine which channels will be followed in varying circumstances. New structure-property relationships for PAHs were also studied. The efficient production of clean energy from fossil fuels will remain a major component of the DOE mission until alternative sources of energy eventually displace coal and petroleum. Hydrocarbons constitute the most basic class of compounds in all of organic chemistry, and as the dominant species in fossil fuels, they figure prominently into the programs of the DOE. Much is already known about the normal chemistry of hydrocarbons under ambient conditions, but far less is known about their intrinsic chemistry at temperatures close to those reached during combustion. An understanding of the fundamental molecular transformations, rearrangements, and interconversions of PAHs at high temperatures in the gas phase, as revealed by careful studies on small, well-designed, molecular systems, provides insights into the underlying chemistry of many important processes that are more complex, such as the generation of energy by the combustion of fossil fuels, the uncatalyzed gasification and liquefaction of coal, the production of fullerenes in fuel-rich flames, and the formation of soot and carcinogenic pollutants in smoke (e.g., benzo[a]pyrene). The rational control of any of these processes, whether it be the optimization of a desirable process or the minimization of an undesirable one, requires a clear knowledge of the basic chemistry that governs the fate of the species involved. Advances in chemistry at the most fundamental level come about primarily from the discovery of new reactions and from new insights into how reactions occur. Harnessing that knowledge is the key to new technologies. The recent commercialization of a combustion

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

OpenAIRE

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

2017-01-01

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

Consumers' Reaction towards Involvement of Large Retailers in ...

African Journals Online (AJOL)

User

markets, fair trade products need LRs distribution channels and not the old system of using speciality ... analysis employed to identify customers' reaction to large retailers' involvement in selling ...... The Journal of Socio-Economics. Vol. 37: pp.

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

International Nuclear Information System (INIS)

Saraeva, V.V.

1986-01-01

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

Motor fuels by hydrogenation of liquid hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1938-05-07

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

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

KAUST Repository

Raj, Abhijeet

2012-02-01

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

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

Science.gov (United States)

Ganguly, Biswa

2009-10-01

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

Recovery of hydrocarbon oils

Energy Technology Data Exchange (ETDEWEB)

1941-02-10

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

Early events following radiolytic and photogeneration of radical cations in hydrocarbons

International Nuclear Information System (INIS)

Werst, D.W.; Trifunac, A.D.

1992-01-01

Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials

Direct electroreduction of CO2 into hydrocarbon

International Nuclear Information System (INIS)

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

2006-01-01

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

Process of converting phenols into hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Seelig, S

1929-02-02

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

Near wall combustion modeling in spark ignition engines. Part B: Post-flame reactions

International Nuclear Information System (INIS)

Demesoukas, Sokratis; Caillol, Christian; Higelin, Pascal; Boiarciuc, Andrei; Floch, Alain

2015-01-01

Highlights: • Models for the post flame reactions (CO and hydrocarbons) and heat release rate are proposed. • ‘Freezing’ effect of CO kinetics is captured but equilibrium CO concentrations are low. • Reactive–diffusive processes are modeled for hydrocarbons and the last stage of combustion is captured. - Abstract: Reduced fuel consumption, low pollutant emissions and adequate output performance are key features in the contemporary design of spark ignition engines. Zero-dimensional numerical simulation is an attractive alternative to engine experiments for the evaluation of various engine configurations. Both flame front reaction and post-flame processes contribute to the heat release rate. The contribution of this work is to highlight and model the role of post-flame reactions (CO and hydrocarbons) in the heat release rate. The modeling approach to CO kinetics used two reactions considered to be dominant and thus more suitable for the description of CO chemical mechanism. Equilibrium concentrations of all the species involved were calculated by a two-zone thermodynamic model. The computed characteristic time of CO kinetics was found to be of a similar order to the results of complex chemistry simulations. The proposed model captured the ‘freezing’ effect (reaction rate is almost zero) for temperatures lower than 1800 K and followed the trends of the measured values at exhaust. However, a consistent underestimation of CO levels at the exhaust was observed. The impact of the remaining CO on the combustion efficiency is considerable especially for rich mixtures. For a remaining 0.4% CO mass fraction, the impact on combustion inefficiency is 0.1%. Unburnt hydrocarbon, which have not reacted within the flame front before quenching, diffuse in the burnt gas and react. In this work, a global reaction rate models the kinetic behavior of hydrocarbon. The diffusion process was modeled by a relaxation equation applied on the calculated kinetic concentration

Process for treating hydrocarbons, etc

Energy Technology Data Exchange (ETDEWEB)

1933-09-15

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

Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

International Nuclear Information System (INIS)

Westbrook, C.K.

2000-01-01

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

A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

DEFF Research Database (Denmark)

1999-01-01

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

On the thermalization achieved in the reactions involving superheavy nuclei

Energy Technology Data Exchange (ETDEWEB)

Bansal, Rajni [Department of Physics, MCM DAV College for Women, Sector 36A, Chandigarh-160036, India rajnibansal.pu@gmail.com (India)

2016-05-06

In the present study, we aim to explore the role of Coulomb potential on the thermalization achieved in the reactions involving superheavy nuclei. Particularly, we shall study the degree of the equilibrium attained in a reaction by the 3D density plots, anisotropy ratio as well as by the rapidity distribution of the nucleons. Our study reveals that the degree of the equilibrium attained in the central reactions of the superheavy nuclei remains unaffected by the Coulomb potential.

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

International Nuclear Information System (INIS)

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

1997-01-01

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

Conversion of hydrocarbon oils into motor fuels

Energy Technology Data Exchange (ETDEWEB)

1937-11-09

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

Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

Energy Technology Data Exchange (ETDEWEB)

Lin, M.C. [Emory Univ., Atlanta, GA (United States)

1993-12-01

Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

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

Energy Technology Data Exchange (ETDEWEB)

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

1980-09-01

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

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

Science.gov (United States)

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

2002-10-01

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

Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and ...

African Journals Online (AJOL)

The kinetic study of coupled gas-iron reactions at 15600 has been carried out for the system involving liquid iron containing carbon and silicon and a gas phase consisting carbon monoxide, silicon monoxide and carbon dioxide. The coupled reactions are: (1) 200(g) = CO2 + C. (2) SiO (g) + CO (g) = Si ¸ CO (g). (3) SiO (g) + ...

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

Science.gov (United States)

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

2000-01-01

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

Biodegradation of petroleum hydrocarbons at low temperatures

International Nuclear Information System (INIS)

Whyte, L. G.; Greer, C W.

1999-01-01

Bioremediation of contaminated Arctic sites has been proposed as the logistically and economically most favorable solution despite the known technical difficulties. The difficulties involve the inhibition of pollutants removal by biodegradation below freezing temperatures and the relative slowness of the process to remove enough hydrocarbon pollutants during the above-freezing summer months. Despite these formidable drawbacks, biodegradation of hydrocarbon contaminants is possible even in below-zero temperatures, especially if indigenous psychrophilic and psychrotropic micro-organism are used. This paper reports results of a study involving several hydrocarbon-degrading psychrotropic bacteria and suggests bioaugmentation with specific cold-adapted organisms and/or biostimulation with commercial fertilizers for enhancing degradation of specific contaminants in soils from northern Canada. An evaluation of the biodegradation potential of hydrocarbon contaminated soils in the high Arctic suggested that the contaminated soils contained sufficient numbers of cold-adapted hydrocarbon-degrading bacteria and that the addition of fertilizer was sufficient to enhance the level of hydrocarbon degradation at low ambient summer temperatures. 9 refs., 2 tabs., 3 figs

Imaging fluid/solid interactions in hydrocarbon reservoir rocks.

Science.gov (United States)

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

1993-08-01

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

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.

Ion-molecular reactions initiated by β-decay of tritium in tritiated compounds

International Nuclear Information System (INIS)

Akulov, G.P.

1976-01-01

Ion-molecular reactions initiated by β-decay of tritium and tritiated hydrocarbons have been systematized. The review describes the theoretical and experimental foundation of the radiochemical method of this important type of chemical interactions investigation. The reactions of the molecular ions of HeT + with methane, ethane, propane, butane and also with cycloalkanes from C 3 to C 6 are discussed. The reactions under consideration have been united into two groups: reactions involving HeT + ions and those involving carbonic ions. From the experimental results available, the conclusions have been drawn about the reactivity of these intermediate formations, about the mechanism of their interaction with organic substances, and also about the perspectives of using the radiochemical method in studies of ion-molecular reactions. The experimental results published before May 1974 are examined. The bibliography includes 162 references

Catalytic cracking of hydrocarbon oils

Energy Technology Data Exchange (ETDEWEB)

1940-09-12

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

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

Science.gov (United States)

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

2012-10-02

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

Investigation of Maillard reaction involvement in the steam ...

African Journals Online (AJOL)

Purpose: To explore the possible mechanism of Maillard reaction (MR) involvement in the steam processing of Panax notoginseng (PN) root. Methods: PN root was soaked in water for 24 h and then steamed at 100 °C using an autoclave for 1, 2, 3, 4, 5 and 6 h, respectively. Several indicators associated with MR during ...

First principles modeling of hydrocarbons conversion in non-equilibrium plasma

Energy Technology Data Exchange (ETDEWEB)

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

2001-07-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-12-05

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

Catalytic and Gas-Solid Reactions Involving HCN over Limestone

DEFF Research Database (Denmark)

Jensen, Anker; Johnsson, Jan Erik; Dam-Johansen, Kim

1997-01-01

In coal-fired combustion systems solid calcium species may be present as ash components or limestone added to the combustion chamber. In this study heterogeneous reactions involving HCN over seven different limestones were investigated in a laboratory fixed-bed quartz reactor at 873-1,173 K...

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

Science.gov (United States)

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

2017-01-25

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

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

Science.gov (United States)

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

1980-01-01

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

Towards comprehensive hydrocarbons analysis of middle distillates by LC-GCxGC.

Science.gov (United States)

Adam, Frédérick; Bertoncini, Fabrice; Thiébaut, Didier; Esnault, Sébastien; Espinat, Didier; Hennion, M C

2007-01-01

The detailed characterization of middle distillates is essential for a better understanding of reactions involved in refining processes. Owing to a higher resolution power and an enhanced sensitivity, but especially to a group-type ordering in the chromatographic plane, comprehensive two-dimensional gas chromatography (GCxGC) offers unsurpassed characterization possibilities for petroleum samples. However, GCxGC fails to totally discriminate naphthenes from unsaturates occurring in hydrotreated diesel samples. This article aims at promoting the implementation of LC-GCxGC for the quantitative determination of hydrocarbon distribution in middle distillates, including naphthenes. In this configuration, liquid chromatography (LC) enables the separation of hydrocarbons into two fractions (viz., saturated and unsaturated) before the subsequent analysis of each fraction by GCxGC. In this paper, the choice of GCxGC conditions in order to achieve the separation and identification of hydrocarbons by chemical class is discussed; under these conditions, naphthenes are separated according to the number of saturated rings. For the first time, the presence of di-, tri-, and tetra-naphthenes resulting from the hydroconversion of aromatics can clearly be evidenced. A quantitative procedure for the determination of the distribution of hydrocarbons, including the distribution of naphthenes according to the number of saturated rings, is also proposed and discussed in detail. LC-GCxGC is found to provide an unequalled degree of information that will widely contribute to a better understanding of hydroconversion processes.

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

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

2016-03-08

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

Catalytic conversion of alcohols to hydrocarbons with low benzene content

Energy Technology Data Exchange (ETDEWEB)

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

2016-09-06

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

Process for scavenging hydrogen sulfide from hydrocarbon gases

International Nuclear Information System (INIS)

Fox, I.

1981-01-01

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

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

Science.gov (United States)

Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando

2017-10-01

Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this

Molecular beam studies of reaction dynamics

International Nuclear Information System (INIS)

Lee, Yuan T.

1991-03-01

The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation

Molecular beam studies of reaction dynamics

Energy Technology Data Exchange (ETDEWEB)

Lee, Y.T. [Lawrence Berkeley Laboratory, CA (United States)

1993-12-01

The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

Hydrocarbon removal with constructed wetlands

OpenAIRE

Eke, Paul Emeka

2008-01-01

Wetlands have long played a significant role as natural purification systems, and have been effectively used to treat domestic, agricultural and industrial wastewater. However, very little is known about the biochemical processes involved, and the use of constructed treatment wetlands in the removal of petroleum aromatic hydrocarbons from produced and/or processed water. Wastewaters from the oil industry contain aromatic hydrocarbons such as benzene, toluene, ethylbenzene and x...

Methods for natural gas and heavy hydrocarbon co-conversion

Science.gov (United States)

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

2009-02-24

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

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1978--February 14, 1979

International Nuclear Information System (INIS)

Rack, E.P.

1979-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, were studied in gaseous, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes and other organic systems in order to better understand the mechanisms and dynamics of high energy monovalent species. The experimental and theoretical program consists of six interrelated areas: (1) the reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure and liquid systems; (2) the gas to condensed state transition in halogen high chemistry, involving bromine activated by the (n,γ) and (I.T.) processes in ethane was investigated in more detail; (3) systematics of halogen hot atom reactions. The reactions of 80 Br/sup m/, 80 Br, 82 Br/sup m/ + 82 Br, 82 Br, 128 I, 130 I, and 130 I/sup m/ + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators; (4) kinetic theory applications of high energy reactions and mathematical development of caging mechanisms were developed; (5) the sterochemistry of 38 Cl substitution reactions involving diastereomeric 1,2-dichloro-1,2-difluorethane in liquid mixtures was completed, suggesting that the stereochemical course of the substitution process is controlled by the properties of the solvent molecules; and (6) the applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems was continued, especially involving aluminum and vanadium trace determinations

Electron transfer reactions involving porphyrins and chlorophyll a

International Nuclear Information System (INIS)

Neta, P.; Scherz, A.; Levanon, H.

1979-01-01

Electron transfer reactions involving porphyrins (P) and quinones (Q) have been studied by pulse radiolysis. The porphyrins used were tetraphenylporphyrin (H 2 TPP), its tetracarboxy derivative (H 2 TCPP), the sodium and zinc compounds (Na 2 TPP and ZnTPP), and chlorophyll a (Chl a). These compounds were found to be rapidly reduced by electron transfer from (CH 3 ) 2 CO - . Reduction by (CH 3 ) 2 COH was rapid in aqueous solutions but relatively slow in i-PrOH solutions. Transient spectra of the anion radicals were determined and, in the case of H 2 TCPP - ., a pK = 9.7 was derived for its protonation. Electron-transfer reactions from the anion radical of H 2 TCPP to benzoquinone, duroquinone, 9,10-anthraquinone 2-sulfonate, and methylviologen occur in aqueous solutions with rate constants approx. 10 7 -10 9 M -1 s -1 which depend on the pH and the quinone reduction potential. Reactions of Na 2 TPP - ., ZnTPP - ., and Chl a - . with anthraquinone in basic i-PrOH solutions occur with rate constants approx. 10 9 M -1 s -1 . The spectral changes associated with these electron-transfer reactions as observed over a period of approx. 1 ms indicated, in some cases, the formation of an intermediate complex [P...Q - .]. 8 figures, 2 tables

A reactive empirical bond order (REBO) potential for hydrocarbon-oxygen interactions

International Nuclear Information System (INIS)

Ni, Boris; Lee, Ki-Ho; Sinnott, Susan B

2004-01-01

The expansion of the second-generation reactive empirical bond order (REBO) potential for hydrocarbons, as parametrized by Brenner and co-workers, to include oxygen is presented. This involves the explicit inclusion of C-O, H-O, and O-O interactions to the existing C-C, C-H, and H-H interactions in the REBO potential. The details of the expansion, including all parameters, are given. The new, expanded potential is then applied to the study of the structure and chemical stability of several molecules and polymer chains, and to modelling chemical reactions among a series of molecules, within classical molecular dynamics simulations

Toluene pyrolysis studies and high temperature reactions of propargyl chloride

Energy Technology Data Exchange (ETDEWEB)

Kern, R.D.; Chen, H.; Qin, Z. [Univ. of New Orleans, LA (United States)

1993-12-01

The main focus of this program is to investigate the thermal decompositions of fuels that play an important role in the pre-particle soot formation process. It has been demonstrated that the condition of maximum soot yield is established when the reaction conditions of temperature and pressure are sufficient to establish a radical pool to support the production of polyaromatic hydrocarbon species and the subsequent formation of soot particles. However, elevated temperatures result in lower soot yields which are attributed to thermolyses of aromatic ring structures and result in the bell-shaped dependence of soot yield on temperature. The authors have selected several acyclic hydrocarbons to evaluate the chemical thermodynamic and kinetic effects attendant to benzene formation. To assess the thermal stability of the aromatic ring, the authors have studied the pyrolyses of benzene, toluene, ethylbenzene, chlorobenzene and pyridine. Time-of-flight mass spectrometry (TOF) is employed to analyze the reaction zone behind reflected shock waves. Reaction time histories of the reactants, products, and intermediates are constructed and mechanisms are formulated to model the experimental data. The TOF work is often performed with use of laser schlieren densitometry (LS) to measure density gradients resulting from the heats of various reactions involved in a particular pyrolytic system. The two techniques, TOF and LS, provide independent and complementary information about ring formation and ring rupture reactions.

Interplay of break-up and transfer processes in reactions involving weakly-bound systems

Science.gov (United States)

Vitturi, Andrea; Moschini, Laura

2018-02-01

In this note we illustrate some applications of a simple model which has been devised to clarify the reaction mechanism and the interplay of different reaction channels (elastic, inelastic, transfer, break-up) in heavy-ion collisions. The model involves two potential wells moving in one dimension and few active particles; in spite of its simplicity, it is supposed to maintain the main features, the properties and the physics of the full three-dimensional case. Special attention is given to the role of continuum states in reactions involving weakly-bound systems, and different approximation schemes (as first-order or coupled-channels) as well as different continuum discretization procedures are tested. In the case of two active particles the reaction mechanism associated with two-particle transfer and the effect of pairing intearction are investigated. Work done in collaboration with Antonio Moro and Kouichi Hagino

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

Science.gov (United States)

Chen, Tao

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

Electrochemical removal of NOx and hydrocarbons

DEFF Research Database (Denmark)

Friedberg, Anja Zarah

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

Syntrophic biodegradation of hydrocarbon contaminants.

Science.gov (United States)

Gieg, Lisa M; Fowler, S Jane; Berdugo-Clavijo, Carolina

2014-06-01

Anaerobic environments are crucial to global carbon cycling wherein the microbial metabolism of organic matter occurs under a variety of redox conditions. In many anaerobic ecosystems, syntrophy plays a key role wherein microbial species must cooperate, essentially as a single catalytic unit, to metabolize substrates in a mutually beneficial manner. Hydrocarbon-contaminated environments such as groundwater aquifers are typically anaerobic, and often methanogenic. Syntrophic processes are needed to biodegrade hydrocarbons to methane, and recent studies suggest that syntrophic hydrocarbon metabolism can also occur in the presence of electron acceptors. The elucidation of key features of syntrophic processes in defined co-cultures has benefited greatly from advances in 'omics' based tools. Such tools, along with approaches like stable isotope probing, are now being used to monitor carbon flow within an increasing number of hydrocarbon-degrading consortia to pinpoint the key microbial players involved in the degradative pathways. The metagenomic sequencing of hydrocarbon-utilizing consortia should help to further identify key syntrophic features and define microbial interactions in these complex communities. Copyright © 2013 Elsevier Ltd. All rights reserved.

Detailed determination of the fusion nuclear radius in reactions involving weakly bound projectiles

International Nuclear Information System (INIS)

Gomez Camacho, A.; Aguilera, E. F.; Quiroz, E. M.

2007-01-01

A detailed determination of the fusion radius parameter is performed within the Distorted Wave Born Approximation for reactions involving weakly bound projectiles. Specifically, a simultaneous X 2- analysis of elastic and fusion cross section data is done using a Woods-Saxon potential with volume and surface parts. The volume part is assumed to be responsible for fusion reactions while the surface part for all other direct reactions. It is proved that in order to fit fusion data, particularly for energies below the Coulomb barrier where fusion is enhanced, it is necessary to have a value of around 1.4 fm for the fusion radial parameter of the fusion potential (W F ). This value is much higher than that frequently used in Barrier Penetration models (1.0 fm). The calculations are performed for reactions involving the weakly bound projectile 9 Be with several medium mass targets. (Author)

Effects of hydrocarbon contamination on ozone generation with dielectric barrier discharges

Science.gov (United States)

Lopez, Jose L.; Vezzu, Guido; Freilich, Alfred; Paolini, Bernhard

2013-08-01

The increasing usage of the feed gases of lower grade liquid oxygen (LOX) containing higher levels of trace hydrocarbon impurities in dielectric barrier discharge (DBD) for ozone generation requires a better understanding of the kinetics of the by-product formation resulting from reactions involving these hydrocarbon impurities. As a case study of hydrocarbon impurities, the kinetics of CH4 conversion in DBDs and the subsequent HNO3 formation were investigated by means of gas-phase plasma diagnostics, supported by detailed process modeling, and extensive in-situ and ex-situ by-product analysis. The by-products formation in the plasma with the presence of CH4, were found to differ significantly in oxygen-fed generators as compared to generators fed with oxygen/nitrogen mixtures. The amount of HNO3 formed depends on the concentration of NOx formed in the plasma and the amount of CH4 that is converted, but not on the O3 concentration. In the present work we have investigated CH4 concentrations of up to 1.95 wt% of the feed gas. The rate of deterioration of the overall ozone generator performance was found to be affected by the concentration of nitrogen in the oxygen/nitrogen mixture.

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

Microbial production of gaseous hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Fukuda, Hideo

1987-10-20

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

Catalytic treatment of hydrocarbon oils

Energy Technology Data Exchange (ETDEWEB)

1940-02-23

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Insights into hydrocarbon formation by nitrogenase cofactor homologs.

Science.gov (United States)

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

2015-04-14

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

Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

International Nuclear Information System (INIS)

Ahmed, I.I.; Gupta, A.K.

2012-01-01

Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

Formation of polycyclic aromatic hydrocarbons by ionizing radiations

International Nuclear Information System (INIS)

Perez, G.; Lilia, E.; Cristalli, A.

1986-01-01

Gaseous 0-terphenyl, 1-phenylnaphthalene, and 9-phenylanthracene were submitted to gamma rays. The yields of cyclization products, polycyclic aromatic hydrocarbons, show that at least one twentieth of the intermediates formed undergo intramolecular reaction. (author)

kinetics of the coupled gas-iron reactions involving silicon and carbon

African Journals Online (AJOL)

user

1985-09-01

Sep 1, 1985 ... out for the system involving liquid iron containing carbon and silicon and a gas ... in content with liquid iron at. 15600C, the ... of carbon monoxide bubbles at the. Slag - metal ..... equilibrium strongly make chemical reactions.

Modification of Catalysts for Steam Reforming of Fluid Hydrocarbons. Research of Gas-Dynamic Duct Cooling Using Planar and Framework Catalysts (CD-ROM)

National Research Council Canada - National Science Library

Kuranov, Alexander L

2005-01-01

.... One way of fuel conversion is the catalytic steam reforming of hydrocarbon. This reaction has a large heat capacity and gives maximum quantity of molecular hydrogen among known reactions of hydrocarbons...

Titanocene-Mediated Dinitrile Coupling: A Divergent Route to Nitrogen-Containing Polycyclic Aromatic Hydrocarbons.

Science.gov (United States)

Kiel, Gavin R; Samkian, Adrian E; Nicolay, Amélie; Witzke, Ryan J; Tilley, T Don

2018-02-21

A general synthetic strategy for the construction of large, nitrogen-containing polycyclic aromatic hydrocarbons (PAHs) is reported. The strategy involves two key steps: (1) a titanocene-mediated reductive cyclization of an oligo(dinitrile) precursor to form a PAH appended with di(aza)titanacyclopentadiene functionality; (2) a divergent titanocene transfer reaction, which allows final-step installation of one or more o-quinone, diazole, or pyrazine units into the PAH framework. The new methodology enables rational, late-stage control of HOMO and LUMO energy levels and thus photophysical and electrochemical properties, as revealed by UV/vis and fluorescence spectroscopy, cyclic voltammetry, and DFT calculations. More generally, this contribution presents the first productive use of di(aza)metallacyclopentadiene intermediates in organic synthesis, including the first formal [2 + 2 + 2] reaction to form a pyrazine ring.

Autothermal reforming of liquid hydrocarbons for H{sub 2} production

Energy Technology Data Exchange (ETDEWEB)

Palm, C.; Montel, S.; Cremer, P.; Peters, R.; Stolten, D. [Forschungszentrum Juelich GmbH (Germany). Inst. for Materials and Processes in Energy Systems IWV-3: Process Engineering

2001-07-01

The process of autothermal reforming of hydrocarbons can be used for the production of hydrogen within a fuel cell system. The application of three precious metal catalysts for the autothermal reforming of alkane mixtures with boiling ranges between 235 and 325 C was examined. The experiments were carried out at n(O{sub 2})/n(C) = 0.40, n(H{sub 2}O)/n(C) = 2.20, a catalyst bed temperature between 730 and 570 C and a hydrocarbon feed of 30 g/h. The catalysts yielded different hydrocarbon conversions, which can be explained by differences in the activity for the steam reforming reaction. The most active catalyst was also successfully utilized in the conversion of 400 g/h hydrocarbon feed. (orig.)

Enhancement of in situ Remediation of Hydrocarbon Contaminated Soil

Energy Technology Data Exchange (ETDEWEB)

Palmroth, M.

2006-07-01

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

Effects of urban air pollution on the inflammatory reaction: involvement of the chemokine pathways; Impact de la pollution atmospherique urbaine sur la reponse inflammatoire: implication des chimiokines

Energy Technology Data Exchange (ETDEWEB)

Fahy, O.

2000-12-01

Urban air pollution is both gaseous and particulate, and diesel exhausts are now the main source of particles. Diesel particles consist of a carbon core with multiple adsorbed organic compounds, among witch poly-aromatic hydrocarbons. These diesel particles and associated poly-aromatic hydrocarbons are likely to play a role in the recent increase in allergic diseases. In this study, we evaluated the effects of diesel organic extracts on the initiation and the orientation of the allergen-dependent inflammatory reaction by analyzing the dis-regulation of a family of mediators involved in cellular recruitment: the chemokines. We demonstrated that mononuclear cells and alveolar macrophages from normal subjects displayed a dis-regulation in pro-inflammatory chemokine expression and production (IL-8, MCP-1, RANTES) when exposed to diesel organic extracts. In addition we observed a synergy between the effects of diesel and allergen when cells from allergic patients were exposed to both simultaneously, leading to a strong over-production of chemokines, and to the increased capacity of recruiting effector cells such as neutrophils and eosinophils. The MAP kinase pathways seemed largely involved in the transduction of diesel and allergen stimulus, since a specific inhibition almost abolished the dis-regulation of chemokine production. Diesel and allergen also appeared to favour the establishment of a type 2 immune response (pro-allergenic), by preferentially recruiting Th2 lymphocytes via the dis-regulation of chemokine expression (MDC and IP-10). Finally, the humanized SCID mouse model grafted with autologous human skin allowed the in vivo evaluation of a local over-production of chemokine, by analyzing the cellular recruitment in the skin after intra-dermal injection of recombinant chemokines. This model appears useful for the study of the mechanisms of cellular recruitment by chemokines and the potential therapeutic approaches. In conclusion, our study underlines the

Clustering mechanism of oxocarboxylic acids involving hydration reaction: Implications for the atmospheric models

Science.gov (United States)

Liu, Ling; Kupiainen-Määttä, Oona; Zhang, Haijie; Li, Hao; Zhong, Jie; Kurtén, Theo; Vehkamäki, Hanna; Zhang, Shaowen; Zhang, Yunhong; Ge, Maofa; Zhang, Xiuhui; Li, Zesheng

2018-06-01

The formation of atmospheric aerosol particles from condensable gases is a dominant source of particulate matter in the boundary layer, but the mechanism is still ambiguous. During the clustering process, precursors with different reactivities can induce various chemical reactions in addition to the formation of hydrogen bonds. However, the clustering mechanism involving chemical reactions is rarely considered in most of the nucleation process models. Oxocarboxylic acids are common compositions of secondary organic aerosol, but the role of oxocarboxylic acids in secondary organic aerosol formation is still not fully understood. In this paper, glyoxylic acid, the simplest and the most abundant atmospheric oxocarboxylic acid, has been selected as a representative example of oxocarboxylic acids in order to study the clustering mechanism involving hydration reactions using density functional theory combined with the Atmospheric Clusters Dynamic Code. The hydration reaction of glyoxylic acid can occur either in the gas phase or during the clustering process. Under atmospheric conditions, the total conversion ratio of glyoxylic acid to its hydration reaction product (2,2-dihydroxyacetic acid) in both gas phase and clusters can be up to 85%, and the product can further participate in the clustering process. The differences in cluster structures and properties induced by the hydration reaction lead to significant differences in cluster formation rates and pathways at relatively low temperatures.

One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

Science.gov (United States)

Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

2014-02-21

In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

Chemical deactivation of Ag/Al2O3 by sulphur for the selective reduction of NOx using hydrocarbons

International Nuclear Information System (INIS)

Houel, Valerie; Millington, Paul; Pollington, Stephen; Poulston, Stephen; Rajaram, Raj R.; Tsolakis, Athanasios

2006-01-01

The hydrocarbon-SCR activity of Ag/Al 2 O 3 catalysts is severely deactivated after low temperature (350 o C) sulphur ageing in the form of SO 2 exposure. Catalysts aged with SO 2 , NO and hydrocarbon present accumulate a significantly larger amount of SO 4 2- than those aged in the presence of only O 2 , H 2 O and SO 2 when exposed to an equivalent amount of S. Following sulphation of the catalyst most of the sulphur can be removed by a high temperature (600 o C) treatment in the reaction gas. Regeneration in the absence of hydrocarbon is ineffective. The hydrocarbon-SCR activity of the sulphated catalyst using model hydrocarbons such as n-C 8 H 18 can be restored after a high temperature pre-treatment in the reaction gases. However this desulphation process fails to regenerate the hydrocarbon-SCR activity when diesel fuel is used in the activity test. TPR studies show that a major fraction of the sulphur species present in the catalyst is removed by such pre-treatment, but the slight residual amount of sulphur is sufficient to inhibit the activation of the diesel fuel on the Ag catalyst. The nature of the hydrocarbon species present for the hydrocarbon-SCR reaction and during the regeneration strongly influences the activity. In general aromatics such as C 7 H 8 are less effective for reducing NO x and regenerating the sulphated catalyst. (author)

Saturated versus unsaturated hydrocarbon interactions with carbon nanostructures

Directory of Open Access Journals (Sweden)

Deivasigamani eUmadevi

2014-09-01

Full Text Available The interactions of various acyclic and cyclic hydrocarbons in both saturated and unsaturated forms with the carbon nanostructures (CNSs have been explored by using density functional theory (DFT calculations. Model systems representing armchair and zigzag carbon nanotubes (CNTs and graphene have been considered to investigate the effect of chirality and curvature of the CNSs towards these interactions. Results of this study reveal contrasting binding nature of the acyclic and cyclic hydrocarbons towards CNSs. While the saturated molecules show stronger binding affinity in acyclic hydrocarbons; the unsaturated molecules exhibit higher binding affinity in cyclic hydrocarbons. In addition, acyclic hydrocarbons exhibit stronger binding affinity towards the CNSs when compared to their corresponding cyclic counterparts. The computed results excellently corroborate the experimental observations. The interaction of hydrocarbons with graphene is more favourable when compared with CNTs. Bader’s theory of atoms in molecules has been invoked to characterize the noncovalent interactions of saturated and unsaturated hydrocarbons. Our results are expected to provide useful insights towards the development of rational strategies for designing complexes with desired noncovalent interaction involving CNSs.

Hydrocarbon isotope detection by elastic peak electron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Kostanovskiy, I.A., E-mail: kostanovskiyia@gmail.com [National Research University MPEI, Krasnokazarmennaya 14, 111250 Moscow (Russian Federation); Afanas’ev, V.P. [National Research University MPEI, Krasnokazarmennaya 14, 111250 Moscow (Russian Federation); Naujoks, D. [Max-Planck-Institut für Plasmaphysik, Teilinstitut Greifswald, Wendelsteinstraße 1, D-17491 Greifswald (Germany); Mayer, M. [Max-Planck-Institut für Plasmaphysik, D-85748 Garching (Germany)

2015-07-15

Highlights: • PCVD hydrocarbon coatings containing protium or deuterium are analyzed via NRA, ERD, XPS and EPES. • EPES analysis with modern electron energy analyzer SPECS Phoibos 225 shows a clear signal from the hydrogen isotopes. • Different primary energies and scattering angles help to quantify isotope content from EPES spectra. - Abstract: Experimental results on the hydrocarbon isotope analysis by elastic peak electron spectroscopy are presented. Amorphous hydrocarbon samples (a-C:H, a-C:D) are prepared by PCVD and analyzed by nuclear reaction analysis (NRA), elastic recoil detection analysis (ERD), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES). Electron energy spectra show a clear signal from the hydrogen isotopes deuterium and protium. Different incident energies and scattering geometries help to resolve plasmon and elastic energy losses.

Hydrocarbon isotope detection by elastic peak electron spectroscopy

International Nuclear Information System (INIS)

Kostanovskiy, I.A.; Afanas’ev, V.P.; Naujoks, D.; Mayer, M.

2015-01-01

Highlights: • PCVD hydrocarbon coatings containing protium or deuterium are analyzed via NRA, ERD, XPS and EPES. • EPES analysis with modern electron energy analyzer SPECS Phoibos 225 shows a clear signal from the hydrogen isotopes. • Different primary energies and scattering angles help to quantify isotope content from EPES spectra. - Abstract: Experimental results on the hydrocarbon isotope analysis by elastic peak electron spectroscopy are presented. Amorphous hydrocarbon samples (a-C:H, a-C:D) are prepared by PCVD and analyzed by nuclear reaction analysis (NRA), elastic recoil detection analysis (ERD), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES). Electron energy spectra show a clear signal from the hydrogen isotopes deuterium and protium. Different incident energies and scattering geometries help to resolve plasmon and elastic energy losses

Microplasma reforming of hydrocarbons for fuel cell power

Science.gov (United States)

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

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

Formalization of hydrocarbon conversion scheme of catalytic cracking for mathematical model development

Science.gov (United States)

Nazarova, G.; Ivashkina, E.; Ivanchina, E.; Kiseleva, S.; Stebeneva, V.

2015-11-01

The issue of improving the energy and resource efficiency of advanced petroleum processing can be solved by the development of adequate mathematical model based on physical and chemical regularities of process reactions with a high predictive potential in the advanced petroleum refining. In this work, the development of formalized hydrocarbon conversion scheme of catalytic cracking was performed using thermodynamic parameters of reaction defined by the Density Functional Theory. The list of reaction was compiled according to the results of feedstock structural-group composition definition, which was done by the n-d-m-method, the Hazelvuda method, qualitative composition of feedstock defined by gas chromatography-mass spectrometry and individual composition of catalytic cracking gasoline fraction. Formalized hydrocarbon conversion scheme of catalytic cracking will become the basis for the development of the catalytic cracking kinetic model.

Chain chemical reactions during matrix devitrification

International Nuclear Information System (INIS)

Barkalov, I.M.

1980-01-01

Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model.

Science.gov (United States)

Fernández, Israel; Bickelhaupt, F Matthias

2016-12-06

In this Focus Review, we present the application of the so-called Activation Strain Model of chemical reactivity to the Diels-Alder cycloaddition reaction. To this end, representative recent examples have been selected to illustrate the power of this new computational approach to gain a deeper quantitative understanding of this fundamental process in chemistry. We cover a wide range of issues, such as, the "endo-rule", reactivity trends emerging from systematic variation in the reactants' strain, and cycloaddition reactions involving relevant species in material science, that is, fullerenes, polycyclic aromatic hydrocarbons and nanotubes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling of separation and reaction in zeolite membrane reactor for hydroisomerization of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Gora, L.; Jansen, J.C. [Ceramic Membrane Centre, The Pore, DelftChemTech, Delft Univ. of Technology, Delft (Netherlands)

2005-03-01

A zeolite membrane reactor has been developed for the hydroisomerization of hydrocarbons, in which the linear molecules are separated from branched ones on the silicalite-1 membrane prior to conversion of the permeated linear hydrocarbons to equilibrium levels on the catalyst bed. Model studies using C{sub 6} components are conducted. n-C{sub 6} separated from 2MP (selectivity 24) is converted for 72% with 36% selectivity towards di-branched isomers (at 393 K). The results indicate that platinum containing chlorinated alumina/silicalite-1 membrane reactor has a potential in upgrading octane values and offers advantages such as higher efficiency, better process control and lower consumption of energy. (orig.)

Coupling of separation and reaction in zeolite membrane reactor for hydroisomerization of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Gora, L.; Maloncy, M.L.; Jansen, J.C. [Ceramic Membrane Centre, The Pore, DelftChemTech, Delft Univ. of Technology (Netherlands)

2004-07-01

A zeolite membrane reactor has been developed for the hydroisomerization of hydrocarbons, in which the linear molecules are separated from branch ones on the silicalite-1 membrane prior to conversion of the permeated linear hydrocarbons to equilibrium levels on the catalyst bed. A model studies using C6 components are conduct. Separated n-C6 from 2MP (selectivity 24) is converted for 72% with 36% selectivity towards di-branched isomers (at 393 K). The results indicate that platinum containing chlorinated alumina/silicalite-1 membrane reactor has a potential in upgrading octane values and offers advantages such as higher efficiency, better process control and lower consumption of energy. (orig.)

On the impact of olefins and aromatics in the methanol-to-hydrocarbon conversion over H-ZSM-5 catalysts

Energy Technology Data Exchange (ETDEWEB)

Sun, X.; Mueller, S.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

2012-07-01

Methanol-to-hydrocarbons processes using HZSM-5 archetype acidic zeolites or zeotype SAPO-34 catalysts are regarded as a vital suite of conversion technologies to bypass petroleum-based routes for the production of specific fuels and petrochemical commodities. Special significance of the methanol chemistry originates from its versatility enabling selective transformations towards various products. Industry demonstrated successfully implementations of Methanol-To-Gasoline, Methanol-To-Olefin, and Methanol-To-Propylene processes, although the typical single-pass selectivity remained limited and recycling is necessary. Considerable fundamental research efforts both from experimental and computational sides contributed to unravel the underlying complex reaction mechanism. The indirect hydrocarbon pool mechanism, in which Broensted acid sites combined with adsorbed light olefins or lower methylbenzenes act as active centers, is generally accepted to explain the formation of light olefins. As olefin and aromatics populated catalytic sites show different reactivity in terms of activity and selectivity to ethylene or propylene, one could envision optimizing the product distribution by suitable co-feeding of specific hydrocarbons. The present work addresses three questions with an experimental study conducted under realistic MTP operation conditions: (1) How are ethylene and propylene formed at molecular level? (2) Which reaction pathway leads to the formation of undesired hydrogen transfer products? (3) Does olefin or aromatics co-feeding change the selectivity to ethylene or propylene? Xylenes and various olefins were co-fed with methanol to achieve a detailed understanding of the reaction mechanism over acidic HZSM-5 zeolites. Results suggest, that an olefin homologation/cracking route (olefin cycle) accounts for the autocatalytic (-like) nature and the majority of methanol consumption rather than the route involving aromatic intermediates (aromatics cycle). Co

Producing light hydrocarbons by destructive hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Fohlen, J H

1928-06-20

A method of obtaining light hydrocarbons from fuels and natural or industrial carbonaceous materials by cracking under pressure from 5 to 200 atmospheres and within a temperature range of 200 to 1,000/sup 0/C, the cracking operation being assisted by the presence of catalysts such as metallic halides, simultaneously, with hydrogenation by means of nascent hydrogen in the reaction chamber.

Stress reactions involving the pars interarticularis in young athletes

Energy Technology Data Exchange (ETDEWEB)

Jackson, D.W.; Wiltse, L.L.; Dingeman, R.D.; Hayes, M.

A stress reaction involving the pars interarticularis of the lumbar spine was confirmed in seven young athletes with a positive technetium pyrophosphate bone scan. No pars defects were detectable on their lumbosacral roentgenograms, which included oblique views. The return to normal levels of radioactive uptake on repeat bone scans correlated closely with their clinical course. If the bony reaction is recognized early, it may heal at a subroentgenographic level and prevent the development of lumbar spondylolysis. These early lesions usually show unilateral increased uptake at one lumbar level on the bone scan and, initially, the athlete localizes the pain to the corresponding unilateral lumbar paraspinous area. The ''one-legged hyperextension test'' is positive on the ipsilateral side and aggravates the pain. Treatment consists of avoiding the aggravating activities and resting. The average time for return to pain-free competition was 7.3 months. These developing defects may be the source of considerable prolonged disability in the young athlete, particularly if undiagnosed and untreated.

Stress reactions involving the pars interarticularis in young athletes

International Nuclear Information System (INIS)

Jackson, D.W.; Wiltse, L.L.; Dingeman, R.D.; Hayes, M.

1981-01-01

A stress reaction involving the pars interarticularis of the lumbar spine was confirmed in seven young athletes with a positive technetium pyrophosphate bone scan. No pars defects were detectable on their lumbosacral roentgenograms, which included oblique views. The return to normal levels of radioactive uptake on repeat bone scans correlated closely with their clinical course. If the bony reaction is recognized early, it may heal at a subroentgenographic level and prevent the development of lumbar spondylolysis. These early lesions usually show unilateral increased uptake at one lumbar level on the bone scan and, initially, the athlete localizes the pain to the corresponding unilateral lumbar paraspinous area. The ''one-legged hyperextension test'' is positive on the ipsilateral side and aggravates the pain. Treatment consists of avoiding the aggravating activities and resting. The average time for return to pain-free competition was 7.3 months. These developing defects may be the source of considerable prolonged disability in the young athlete, particularly if undiagnosed and untreated

In-situ hydrocarbon delineation using laser-induced fluorescence

International Nuclear Information System (INIS)

Taer, A.D.; Hastings, R.W.; Brown, A.Y.; Frend, R.

1996-01-01

An investigation of hydrocarbons in soils was conducted at an active Shell Oil Company petroleum products terminal, located in Carson, California. An investigation approach involving Laser-Induced Fluorescence (LIF) and Cone Penetrometer Testing (CPT) technologies was implemented to provide real-time, in-situ characterization of site stratigraphy, hydrocarbon distribution and importantly, hydrocarbon product differentiation. The area of investigation is located along a property boundary, where a plume of separate phase hydrocarbons has been actively recovered for several years. CPT/LIF technology was selected for the investigation since previous delineation efforts using hydrocarbon fingerprinting methods proved inconclusive. Additionally, the CPT/LIF technology had the potential to provide a cost effective solution to accomplish project objectives. Based on the information obtained during this investigation, it was determined that the plume of separate phase hydrocarbons along the northern property boundary is from a source distinctly different than any identified hydrocarbons known to be from on-site sources. In addition, the plume was determined to not be connected with any other known on-site hydrocarbon plumes. The results of this CPT/LIF investigation were consistent with the known hydrogeologic conditions. This evaluation determined that CPT/LIF technology was very effective in addressing project objectives and resulted in a significant cost savings

Field desorption mass spectroscopy monitoring of changes in hydrocarbon type composition during petroleum biodegradation

International Nuclear Information System (INIS)

Huesemann, M.H.

1995-01-01

A comprehensive petroleum hydrocarbon characterization procedure involving group type separation, boiling point distribution, and hydrocarbon typing by field desorption mass spectroscopy (FDMS) has been developed to quantify changes in hydrocarbon type composition during bioremediation of petroleum-contaminated soils. FDMS is able to quantify the concentration of hundreds of specific hydrocarbon types based on their respective hydrogen deficiency (z-number) and molecular weight (carbon number). Analytical results from two bioremediation experiments involving soil contaminated with crude oil and motor oil indicate that alkanes and two-ring saturates (naphthenes) were readily biodegradable. In addition, low-molecular-weight hydrocarbons generally were biodegraded to a larger extent than those of high molecular weight. More importantly, it was found that the extent of biodegradation of specific hydrocarbon types was comparable between treatments and appeared to be unaffected by the petroleum contaminant source, soil type, or experimental conditions. It was therefore concluded that in these studies the extent of total petroleum hydrocarbon (TPH) biodegradation is primarily affected by the molecular composition of the petroleum hydrocarbons present in the contaminated soil

Automatic reduction of the hydrocarbon reaction mechanisms in fusion edge plasmas

International Nuclear Information System (INIS)

Dauwe, A.; Tytgadt, M.; Reiter, D.; Baelmans, M.

2006-11-01

For predictions of the tritium inventory in future fusion devices like ITER, the amount of eroded carbon and the hydrogen concentrations in co-deposited hydrocarbon layers have to be predicted quantitatively. Predictions about the locations of co-deposited layers are also necessary in order to design deposition diagnostics and layer removal methods. This requires a detailed physical understanding of the erosion and carbon migration processes, and computer simulations. For accurate simulation the multi-species code EIRENE would require to include over 50 participating species. Because such a calculation is computationally prohibitive current codes are being reduced, typically in an ad hoc fashion. In this work the potential of the mathematically sound method of intrinsic low dimensional manifolds (ILDM) for computational speed-up of the hydrocarbon transport problem simulation is thoroughly investigated. It is basically the Monte Carlo implementation of EIRENE that makes this task so challenging. As the method can substantially ameliorate the results in comparison to the conventional reduction mechanisms a step towards ILDM-reduced kinetics is conceived and tested. (orig.)

On the role of resonantly stabilized radicals in polycyclic aromatic hydrocarbon (PAH) formation: pyrene and fluoranthene formation from benzyl-indenyl addition.

Science.gov (United States)

Sinha, Sourab; Rahman, Ramees K; Raj, Abhijeet

2017-07-26

Resonantly stabilized radicals, such as propargyl, cyclopentadienyl, benzyl, and indenyl, play a vital role in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) that are soot precursors in engines and flames. Pyrene is considered to be an important PAH, as it is thought to nucleate soot particles, but its formation pathways are not well known. This paper presents a reaction mechanism for the formation of four-ring aromatics, pyrene and fluoranthene, through the combination of benzyl and indenyl radicals. The intermediate species and transition structures involved in the elementary reactions of the mechanism were studied using density functional theory, and the reaction kinetics were evaluated using transition state theory. The barrierless addition of benzyl and indenyl to form the adduct, 1-benzyl-1H-indene, was found to be exothermic with a reaction energy of 204.2 kJ mol -1 . The decomposition of this adduct through H-abstraction and H 2 -loss was studied to determine the possible products. The rate-of-production analysis was conducted to determine the most favourable reactions for pyrene and fluoranthene formation. The premixed laminar flames of toluene, ethylbenzene, and benzene were simulated using a well-validated hydrocarbon fuel mechanism with detailed PAH chemistry after adding the proposed reactions to it. The computed and experimentally observed species profiles were compared to determine the effect of the new reactions for pyrene and fluoranthene formation on their concentration profiles. The role of benzyl and indenyl combination in PAH formation and growth is highlighted.

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

Science.gov (United States)

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

2018-03-01

The n-propyl + O2 reaction is an important model of chain branching reactions in larger combustion systems. In this work, focal point analyses (FPAs) extrapolating to the ab initio limit were performed on the n-propyl + O2 system based on explicit quantum chemical computations with electron correlation treatments through coupled cluster single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] and basis sets up to cc-pV5Z. All reaction species and transition states were fully optimized at the rigorous CCSD(T)/cc-pVTZ level of theory, revealing some substantial differences in comparison to the density functional theory geometries existing in the literature. A mixed Hessian methodology was implemented and benchmarked that essentially makes the computations of CCSD(T)/cc-pVTZ vibrational frequencies feasible and thus provides critical improvements to zero-point vibrational energies for the n-propyl + O2 system. Two key stationary points, n-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1), were located 32.7 kcal mol-1 and 2.4 kcal mol-1 below the reactants, respectively. Two competitive β-hydrogen transfer transition states (TS2 and TS2') were found separated by only 0.16 kcal mol-1, a fact unrecognized in the current combustion literature. Incorporating TS2' in master equation (ME) kinetic models might reduce the large discrepancy of 2.5 kcal mol-1 between FPA and ME barrier heights for TS2. TS2 exhibits an anomalously large diagonal Born-Oppenheimer correction (ΔDBOC = 1.71 kcal mol-1), which is indicative of a nearby surface crossing and possible nonadiabatic reaction dynamics. The first systematic conformational search of three hydroperoxypropyl (QOOH) intermediates was completed, uncovering a total of 32 rotamers lying within 1.6 kcal mol-1 of their respective lowest-energy minima. Our definitive energetics for stationary points on the n-propyl + O2 potential energy surface provide key benchmarks for future studies

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

KAUST Repository

Raj, Abhijeet

2012-11-01

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

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

KAUST Repository

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

2012-01-01

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

Kynurenine pathway metabolites and enzymes involved in redox reactions.

Science.gov (United States)

González Esquivel, D; Ramírez-Ortega, D; Pineda, B; Castro, N; Ríos, C; Pérez de la Cruz, V

2017-01-01

Oxido-reduction reactions are a fundamental part of the life due to support many vital biological processes as cellular respiration and glucose oxidation. In the redox reactions, one substance transfers one or more electrons to another substance. An important electron carrier is the coenzyme NAD + , which is involved in many metabolic pathways. De novo biosynthesis of NAD + is through the kynurenine pathway, the major route of tryptophan catabolism, which is sensitive to redox environment and produces metabolites with redox capacity, able to alter biological functions that are controlled by redox-responsive signaling pathways. Kynurenine pathway metabolites have been implicated in the physiology process and in the physiopathology of many diseases; processes that also share others factors as dysregulation of calcium homeostasis, mitochondrial dysfunction, oxidative stress, inflammation and cell death, which impact the redox environment. This review examines in detail the available evidence in which kynurenine pathway metabolites participate in redox reactions and their effect on cellular redox homeostasis, since the knowledge of the main factors and mechanisms that lead to cell death in many neurodegenative disorders and other pathologies, such as mitochondrial dysfunction, oxidative stress and kynurenines imbalance, will allow to develop therapies using them as targets. This article is part of the Special Issue entitled 'The Kynurenine Pathway in Health and Disease'. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles

Science.gov (United States)

Merino-Garcia, I.; Albo, J.; Irabien, A.

2018-01-01

Copper-based surfaces appear as the most active catalysts for CO2 electroreduction to hydrocarbons, even though formation rates and efficiencies still need to be improved. The aim of the present work is to evaluate the continuous gas-phase CO2 electroreduction to hydrocarbons (i.e. ethylene and methane) at copper nanoparticulated-based surfaces, paying attention to particle size influence (ranging from 25-80 nm) on reaction productivity, selectivity, and Faraday efficiency (FE) for CO2 conversion. The effect of the current density and the presence of a microporous layer within the working electrode are then evaluated. Copper-based gas diffusion electrodes are prepared by airbrushing the catalytic ink onto carbon supports, which are then coupled to a cation exchange membrane (Nafion) in a membrane electrode assembly. The results show that the use of smaller copper nanoparticles (25 nm) leads to a higher ethylene production (1148 μmol m-2 s-1) with a remarkable high FE (92.8%), at the same time, diminishing the competitive hydrogen evolution reaction in terms of FE. This work demonstrates the importance of nanoparticle size on reaction selectivity, which may be of help to design enhanced electrocatalytic materials for CO2 valorization to hydrocarbons.

Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

Energy Technology Data Exchange (ETDEWEB)

Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

1993-12-01

Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

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)

Casey, C.P.

1985-02-01

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 n 5 - and n'-C 5 H 5 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

Selective transformation of syngas into gasoline-range hydrocarbons over mesoporous H-ZSM-5-supported cobalt nanoparticles.

Science.gov (United States)

Cheng, Kang; Zhang, Lei; Kang, Jincan; Peng, Xiaobo; Zhang, Qinghong; Wang, Ye

2015-01-26

Bifunctional Fischer-Tropsch (FT) catalysts that couple uniform-sized Co nanoparticles for CO hydrogenation and mesoporous zeolites for hydrocracking/isomerization reactions were found to be promising for the direct production of gasoline-range (C5-11 ) hydrocarbons from syngas. The Brønsted acidity results in hydrocracking/isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the mesoporosity contributes to suppressing the formation of lighter (C1-4 ) hydrocarbons. The selectivity for C5-11 hydrocarbons could reach about 70 % with a ratio of isoparaffins to n-paraffins of approximately 2.3 over this catalyst, and the former is markedly higher than the maximum value (ca. 45 %) expected from the Anderson-Schulz-Flory distribution. By using n-hexadecane as a model compound, it was clarified that both the acidity and mesoporosity play key roles in controlling the hydrocracking reactions and thus contribute to the improved product selectivity in FT synthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of molybdenum borides by combustion synthesis involving solid-phase displacement reactions

International Nuclear Information System (INIS)

Yeh, C.L.; Hsu, W.S.

2008-01-01

Preparation of molybdenum borides of five different phases in the Mo-B binary system (including Mo 2 B, MoB, MoB 2 , Mo 2 B 5 , and MoB 4 ) was performed by self-propagating high-temperature synthesis (SHS) with two kinds of the reactant samples. When elemental powder compacts with an exact stoichiometry corresponding to the boride phase were employed, self-sustaining reaction was only achieved in the sample with Mo:B = 1:1 and nearly single-phase MoB was yielded. Therefore, the other four boride compounds were prepared from the reactant compacts composed of MoO 3 , Mo, and B powders, within which the displacement reaction of MoO 3 with boron was involved in combustion synthesis. Experimental evidence shows that the extent of displacement reaction in the overall reaction has a significant impact on sustainability of the synthesis reaction, combustion temperature, reaction front velocity, and composition of the end product. An increase in the solid-phase displacement reaction taking place during the SHS process contributes more heat flux to the synthesis reaction, thus resulting in the increase of combustion temperature and enhancement of the reaction front velocity. Based upon the XRD analysis, formation of Mo 2 B, MoB 2 , and Mo 2 B 5 as the dominant boride phase in the end product was successful through the SHS reaction with powder compacts under appropriate stoichiometries between MoO 3 , Mo, and B. However, a poor conversion was observed in the synthesis of MoB 4 . The powder compact prepared for the production of MoB 4 yielded mostly Mo 2 B 5

A method for predicting the extent of petroleum hydrocarbon biodegradation in contaminated soils

International Nuclear Information System (INIS)

Huesemann, M.H.

1994-01-01

A series of solid- and slurry-phase soil bioremediation experiments involving different crude oils and refined petroleum products were performed to investigate the factors which affect the maximum extent of total petroleum hydrocarbon (TPH) biodegradation. The authors used a comprehensive petroleum hydrocarbon characterization procedure involving group-type separation analyses, boiling-point distributions, and hydrocarbon typing by field ionization mass spectroscopy. Initial and final concentrations of specified hydrocarbon classes were determined in each of seven different bioremediation treatments. Generally, they found that the degree of TPH biodegradation was affected mainly by the type of hydrocarbons in the contaminant matrix. In contrast, the influence of experimental variables such as soil type, fertilizer concentrations, microbial plate counts, and treatment type (slurry versus landfarming) on the overall extent of TPH biodegradation was insignificant. Based on these findings, a predictive algorithm was developed to estimate the extent of TPH biodegradation from the average reduction of 86 individual hydrocarbon classes and their respective initial concentrations. Model predictions for gravimetric TPH removals were in close agreement with analytical results from two independent laboratories

Electron microscopy of hydrocarbon production in parthenium argentatum (guayule)

Energy Technology Data Exchange (ETDEWEB)

Bauer, Thomas E. [Univ. of California, Berkeley, CA (United States)

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.

Aromatic hydrocarbons

International Nuclear Information System (INIS)

Roder, M.

1985-01-01

Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

Using Ionic Liquids in Selective Hydrocarbon Conversion Processes

Energy Technology Data Exchange (ETDEWEB)

Tang, Yongchun; Periana, Roy; Chen, Weiqun; van Duin, Adri; Nielsen, Robert; Shuler, Patrick; Ma, Qisheng; Blanco, Mario; Li, Zaiwei; Oxgaard, Jonas; Cheng, Jihong; Cheung, Sam; Pudar, Sanja

2009-09-28

This is the Final Report of the five-year project Using Ionic Liquids in Selective Hydrocarbon Conversion Processes (DE-FC36-04GO14276, July 1, 2004- June 30, 2009), in which we present our major accomplishments with detailed descriptions of our experimental and theoretical efforts. Upon the successful conduction of this project, we have followed our proposed breakdown work structure completing most of the technical tasks. Finally, we have developed and demonstrated several optimized homogenously catalytic methane conversion systems involving applications of novel ionic liquids, which present much more superior performance than the Catalytica system (the best-to-date system) in terms of three times higher reaction rates and longer catalysts lifetime and much stronger resistance to water deactivation. We have developed in-depth mechanistic understandings on the complicated chemistry involved in homogenously catalytic methane oxidation as well as developed the unique yet effective experimental protocols (reactors, analytical tools and screening methodologies) for achieving a highly efficient yet economically feasible and environmentally friendly catalytic methane conversion system. The most important findings have been published, patented as well as reported to DOE in this Final Report and our 20 Quarterly Reports.

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.

To address surface reaction network complexity using scaling relations machine learning and DFT calculations

International Nuclear Information System (INIS)

Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas; Nørskov, Jens K.

2017-01-01

Surface reaction networks involving hydrocarbons exhibit enormous complexity with thousands of species and reactions for all but the very simplest of chemistries. We present a framework for optimization under uncertainty for heterogeneous catalysis reaction networks using surrogate models that are trained on the fly. The surrogate model is constructed by teaching a Gaussian process adsorption energies based on group additivity fingerprints, combined with transition-state scaling relations and a simple classifier for determining the rate-limiting step. The surrogate model is iteratively used to predict the most important reaction step to be calculated explicitly with computationally demanding electronic structure theory. Applying these methods to the reaction of syngas on rhodium(111), we identify the most likely reaction mechanism. Lastly, propagating uncertainty throughout this process yields the likelihood that the final mechanism is complete given measurements on only a subset of the entire network and uncertainty in the underlying density functional theory calculations.

Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom

Science.gov (United States)

2016-04-05

acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H.sup. ions for Na.sup. ions. Carbon dioxide may be...extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide . The carbon dioxide and hydrogen may be used to produce hydrocarbons.

Staff's reactions towards partnered sexual expressions involving people with dementia living in long-term care facilities.

Science.gov (United States)

Villar, Feliciano; Celdrán, Montserrat; Serrat, Rodrigo; Fabà, Josep; Martínez, Teresa

2018-05-01

To explore staff responses, in terms of common practices, towards partnered sexual relationships in long-term care facilities where one or both people involved have dementia. It also tries to determine personal and institutional factors influencing these responses. Although some studies, mostly qualitative, have focused on reactions to residents' sexual expressions so far the issue has not been assessed in a study using large and diverse samples. Cross-sectional quantitative study using vignette technique. Participants were 2,295 staff members at 152 Spanish long-term care facilities. Data were collected during 2016. A vignette describing sexual situations involving people with dementia was presented to participants. After the vignette, participants had to answer the question: "What do you think most of your colleagues would do in this situation?" with nine possible responses. Results showed that relationships involving persons with dementia were perceived as potentially problematic by staff. In both conditions, discussing the case with a colleague or supervisor was the most frequently chosen reaction. More restrictive reactions were mentioned when only one person with dementia was involved in the relationship. Factors such as participants" age and years of experience, professional post and commitment to person-centred care practices were related with the frequency of common restriction practices. Results highlight the importance of providing staff with clear guidelines regarding the management of specific sexual situations to avoid stereotyped restrictive reactions. © 2017 John Wiley & Sons Ltd.

Studies on the production of hydrocarbon mixtures from waste methyl ethyl ketone

International Nuclear Information System (INIS)

Kokitkar, P.B.; Roth, O.B.; Debelak, K.A.

1992-01-01

Large quantities of waste solvents are generated annually around the world in a large number of diverse industries, the paints and plastics industry being the largest consumer. The management of these waste solvents is becoming more and more difficult due to stricter environmental regulations by the EPA. The paint and allied products industry is expected to shift its solvent use from aliphatics and aromatics to oxygenated solvents to meet emissions and disposal standards. Many researchers have studied the dehydration reactions of oxygenated solvents to produce dehydration. However, most researchers have obtained only low molecular weight compounds (C 3 - C 4 hydrocarbons) from C 1 - C 4 alcohols and ketones. The kinetics of this class of reactions are not available in the open literature. The objective of this paper is to investigate the thermodynamic feasibility of this class of reactions and to compare the hydrocarbon products obtained using methylethyl ketone with regular unleaded gasoline

Cross-section and reaction rates for some reactions involved in explosive nucleosynthesis

International Nuclear Information System (INIS)

Cheng, C.W.

1979-03-01

Total proton-induced and alpha-induced reaction cross sections have been determined for the 24 Mg(α,n), 25 Mg(p,n), 26 Mg(p,n), 27 Al(p,n), 28 Si(α,n), 42 Ca(p,γ), 42 Ca(α,n) and 44 Ca(p,n) reactions from energies near threshold (except the exothermic (p,γ) reaction) to about 3 to 4 MeV above threshold. The product nuclei are all positron emitters with half-lives ranging from about 3 sec to about 4 hours. From the measured cross sections reaction rates have been calculated in the temperature range 1 9 9 =1, at which the discrepancy is large. Included also are analytic forms for (p,n), (α,n), and (p,γ) reactions which can be used to describe the reaction rate within the temperature range 1 9 <=6 and which agree with the experimental rates at the discrete temperatures where the reaction rates have been calculated

External heavy atom effect on intersystem crossing reactions of aromatic hydrocarbons

International Nuclear Information System (INIS)

Wojnarovits, L.; Foeldiak, G.

1988-01-01

The external heavy atom effect by xenon on the S 1 → T n and T 1 → S o transitions of naphthalene and pyrene was investigated in hydrocarbon solvents by fluorescence or absorption spectroscopy. The quencher forms a short-lived encounter complex (that may be called exciplex as well) with the excited molecules in equilibrium process. This exciplex formation in solutions with naphthalene leads to some deviation from the Stern-Volmer type concentration dependence of the quenching. (author)

Characterization of cyanobacterial hydrocarbon composition and distribution of biosynthetic pathways.

Directory of Open Access Journals (Sweden)

R Cameron Coates

Full Text Available Cyanobacteria possess the unique capacity to naturally produce hydrocarbons from fatty acids. Hydrocarbon compositions of thirty-two strains of cyanobacteria were characterized to reveal novel structural features and insights into hydrocarbon biosynthesis in cyanobacteria. This investigation revealed new double bond (2- and 3-heptadecene and methyl group positions (3-, 4- and 5-methylheptadecane for a variety of strains. Additionally, results from this study and literature reports indicate that hydrocarbon production is a universal phenomenon in cyanobacteria. All cyanobacteria possess the capacity to produce hydrocarbons from fatty acids yet not all accomplish this through the same metabolic pathway. One pathway comprises a two-step conversion of fatty acids first to fatty aldehydes and then alkanes that involves a fatty acyl ACP reductase (FAAR and aldehyde deformylating oxygenase (ADO. The second involves a polyketide synthase (PKS pathway that first elongates the acyl chain followed by decarboxylation to produce a terminal alkene (olefin synthase, OLS. Sixty-one strains possessing the FAAR/ADO pathway and twelve strains possessing the OLS pathway were newly identified through bioinformatic analyses. Strains possessing the OLS pathway formed a cohesive phylogenetic clade with the exception of three Moorea strains and Leptolyngbya sp. PCC 6406 which may have acquired the OLS pathway via horizontal gene transfer. Hydrocarbon pathways were identified in one-hundred-forty-two strains of cyanobacteria over a broad phylogenetic range and there were no instances where both the FAAR/ADO and the OLS pathways were found together in the same genome, suggesting an unknown selective pressure maintains one or the other pathway, but not both.

Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

KAUST Repository

Liu, Zhaohui; Dong, Xinglong; Liu, Xin; Han, Yu

2016-01-01

Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences

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

DEFF Research Database (Denmark)

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

2004-01-01

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

Charge transfer reactions in Xe plasma expansion

International Nuclear Information System (INIS)

Jiao, C. Q.; Garscadden, A.; Ganguly, B. N.

2007-01-01

Charge transfer reactions of fast Xe ions with hydrocarbons including methane (CH 4 ), ethene (C 2 H 4 ), and propane (C 3 H 8 ) are studied by adding these hydrocarbon gases into a cross flowing Xe plasma expansion. Branching ratios and relative reaction rates for the charge transfers of fast Xe + with each of the three hydrocarbon gases are measured under different rf powers of the inductively coupled Xe discharge. For CH 4 /Xe system, we find that fast Xe + reacts readily with CH 4 generating CH 4 + and CH 3 + in a ratio of 1:0.56, with an estimated rate coefficient of (2.3±0.3)x10 -10 cm 3 /s at 75 W rf power which slowly increases to (2.9±0.3)x10 -10 cm 3 /s at 250 W (error bars reflect only the uncertainties due to the unknown extent of the ion recombination that follows the charge transfer reaction). These observed charge transfer reactions are made possible by the kinetically excited Xe ions produced by free expansion of the plasma. For the C 2 H 4 /Xe system product ions C 2 H 4 + and C 2 H 2 + are observed, and for C 3 H 8 /Xe, C 2 H 4 + and C 2 H 5 + and minor product ions including C 2 H 2 + and C 3 H 7 + are observed

Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

Science.gov (United States)

Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

2014-12-02

Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

Continuous process for converting hydrocarbons, etc

Energy Technology Data Exchange (ETDEWEB)

1934-05-01

A continuous process is disclosed for converting hydrocarbons, liquid, semi-liquid, and solid, of all origins and kinds, into incondensable gases, without carbon deposits, characterized by the fact that an intimate mixture of the material and superheated steam before cracking is passed through a contact mass. The contact mass consists of all metals, metal alloys, and mineral salts which, at the reaction temperature, are fused and do not react with the water vapor or gaseous products.

Microbial hydrocarbon degradation - bioremediation of oil spills

Energy Technology Data Exchange (ETDEWEB)

Atlas, R M [Louisville Univ., KY (United States). Dept. of Biology

1991-01-01

Bioremediation has become a major method employed in restoration of oil-polluted environments that makes use of natural microbial biodegradative activities. Bioremediation of petroleum pollutants overcomes the factors limiting rates of microbial hydrocarbon biodegradation. Often this involves using the enzymatic capabilities of the indigenous hydrocarbon-degrading microbial populations and modifying environmental factors, particularly concentrations of molecular oxygen, fixed forms of nitrogen and phosphate to achieve enhanced rates of hydrocarbon biodegradation. Biodegradation of oily sludges and bioremediation of oil-contaminated sites has been achieved by oxygen addition-e.g. by tilling soils in landfarming and by adding hydrogen peroxide or pumping oxygen into oiled aquifers along with addition of nitrogen- and phosphorous-containing fertilizers. The success of seeding oil spills with microbial preparations is ambiguous. Successful bioremediation of a major marine oil spill has been achieved based upon addition of nitrogen and phosphorus fertilizers. (author).

Quantum chemical investigation of the reaction of O( P2) with certain ...

Indian Academy of Sciences (India)

WINTEC

In the case of methyl radical the minimum energy reaction pathway leads to the products CO + H2 + H. In ... Reactions of atomic oxygen with hydrocarbon radicals play an important role in ..... The reaction between singlet oxygen and propyl ...

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

OpenAIRE

Kleindienst, Sara

2012-01-01

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

Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

Science.gov (United States)

Wilkes, Heinz; Buckel, Wolfgang; Golding, Bernard T; Rabus, Ralf

2016-01-01

The glycyl radical enzyme-catalyzed addition of n-alkanes to fumarate creates a C-C-bond between two concomitantly formed stereogenic carbon centers. The configurations of the two diastereoisomers of the product resulting from n-hexane activation by the n-alkane-utilizing denitrifying bacterium strain HxN1, i.e. (1-methylpentyl)succinate, were assigned as (2S,1'R) and (2R,1'R). Experiments with stereospecifically deuterated n-(2,5-2H2)hexanes revealed that exclusively the pro-S hydrogen atom is abstracted from C2 of the n-alkane by the enzyme and later transferred back to C3 of the alkylsuccinate formed. These results indicate that the alkylsuccinate-forming reaction proceeds with an inversion of configuration at the carbon atom (C2) of the n-alkane forming the new C-C-bond, and thus stereochemically resembles a SN2-type reaction. Therefore, the reaction may occur in a concerted manner, which may avoid the highly energetic hex-2-yl radical as an intermediate. The reaction is associated with a significant primary kinetic isotope effect (kH/kD ≥3) for hydrogen, indicating that the homolytic C-H-bond cleavage is involved in the first irreversible step of the reaction mechanism. The (1-methylalkyl)succinate synthases of n-alkane-utilizing anaerobic bacteria apparently have very broad substrate ranges enabling them to activate not only aliphatic but also alkyl-aromatic hydrocarbons. Thus, two denitrifiers and one sulfate reducer were shown to convert the nongrowth substrate toluene to benzylsuccinate and further to the dead-end product benzoyl-CoA. For this purpose, however, the modified β-oxidation pathway known from alkylbenzene-utilizing bacteria was not employed, but rather the pathway used for n-alkane degradation involving CoA ligation, carbon skeleton rearrangement and decarboxylation. Furthermore, various n-alkane- and alkylbenzene-utilizing denitrifiers and sulfate reducers were found to be capable of forming benzyl alcohols from diverse alkylbenzenes

Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

Science.gov (United States)

Thompson, Matthew G K; Parnis, J Mark

2005-10-27

The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.

Detailed modeling of hydrocarbon nanoparticle nucleation in acetylene discharges

International Nuclear Information System (INIS)

Bleecker, Kathleen de; Bogaerts, Annemie; Goedheer, Wim

2006-01-01

The initial stage of nanoparticle formation and growth in radiofrequency acetylene (C 2 H 2 ) plasmas is investigated by means of a self-consistent one-dimensional fluid model. A detailed chemical kinetic scheme, containing electron impact, ion-neutral, and neutral-neutral reactions, has been developed in order to predict the underlying dust growth mechanisms and the most important dust precursors. The model considers 41 different species (neutrals, radicals, ions, and electrons) describing hydrocarbons (C n H m ) containing up to 12 carbon atoms. Possible routes for particle growth are discussed. Both positive and negative ion reaction pathways are considered, as consecutive anion- and cation-molecule reactions seem to lead to a fast build up of the carbon skeleton

Influence of adhesion on aerobic biodegradation and bioremediation of liquid hydrocarbons.

Science.gov (United States)

Abbasnezhad, Hassan; Gray, Murray; Foght, Julia M

2011-11-01

Biodegradation of poorly water-soluble liquid hydrocarbons is often limited by low availability of the substrate to microbes. Adhesion of microorganisms to an oil-water interface can enhance this availability, whereas detaching cells from the interface can reduce the rate of biodegradation. The capability of microbes to adhere to the interface is not limited to hydrocarbon degraders, nor is it the only mechanism to enable rapid uptake of hydrocarbons, but it represents a common strategy. This review of the literature indicates that microbial adhesion can benefit growth on and biodegradation of very poorly water-soluble hydrocarbons such as n-alkanes and large polycyclic aromatic hydrocarbons dissolved in a non-aqueous phase. Adhesion is particularly important when the hydrocarbons are not emulsified, giving limited interfacial area between the two liquid phases. When mixed communities are involved in biodegradation, the ability of cells to adhere to the interface can enable selective growth and enhance bioremediation with time. The critical challenge in understanding the relationship between growth rate and biodegradation rate for adherent bacteria is to accurately measure and observe the population that resides at the interface of the hydrocarbon phase. © Springer-Verlag 2011

Catalysts for the production of hydrocarbons from carbon monoxide and water

Science.gov (United States)

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

1985-11-06

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

Synthesis of a basket-shaped C56H38 hydrocarbon as a precursor toward an end-cap template for carbon [6,6]nanotubes.

Science.gov (United States)

Cui, Hu; Akhmedov, Novruz G; Petersen, Jeffrey L; Wang, Kung K

2010-03-19

A basket-shaped C(56)H(38) hydrocarbon (3) possessing a 30-carbon difluorenonaphthacenyl core that can be mapped onto the surface of C(78) was synthesized from 4-bromo-1-indanone. The first stage of the synthesis involved the preparation of tetraketone 10 as a key intermediate. The use of cascade cyclization reactions of benzannulated enyne-allenes as key features in the next stage of the synthetic sequence provides an efficient route to 3 from 4-bromo-1-indanone in 12 steps. The all-cis relationship among the methyl groups and the methine hydrogens causes the two benzofluorenyl units in 3 to be in an essentially perpendicular orientation to each other. Hydrocarbon 3 and its derivatives could serve as attractive precursors leading to a geodesic C(68)H(26) end-cap template for carbon [6,6]nanotubes.

Hydrogenating gaseous hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Nicolardot, P L.F.

1930-08-06

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

Analysis of petroleum hydrocarbons in soil from view of bioremediation process

International Nuclear Information System (INIS)

Mracnova, R.; Sojak, L.; Kubinec, R.; Kraus, A.; Eszenyiova, A.; Ostrovsky, I.

2002-01-01

The pollution of the environment by petroleum hydrocarbons is the most often pollution of them all. Nevertheless, hydrocarbons present in environment can be not only of petroleum or anthropogenic origin, but of biogenic as well. Typically the hydrocarbons are presented in the environment as very complex mixtures of individual compounds with very different chemical structure, wide range of the boiling points (∼800 0 C) as well as with the wide range of the number of carbon atoms. Immediately they are spread in any environmental matrix the complex physical, chemical and biochemical reactions start. A lot of methods have been developed and new are permanently in progress for the monitoring and control of petroleum hydrocarbons contamination and/or soils bioremediation. Generally, all methods by whose the hydrocarbons contaminants are determined in GC-FID system do not satisfied recommendations for enough accurate and precise results. Hyphenation of capillary gas chromatography and mass selective detector operated in the selective ion monitoring mode essentially allows detailed specification of non-polar extractable hydrocarbons. Isoprenoid alkanes, alkylhomologues of aromatic hydrocarbons and polycyclic alkanes hopanes-like were investigated as markers for recognition of petroleum and biogenic contamination. C 30 17α(H)21β(H)-hopane (C 30 -hopane) seems to be a suitable marker to identify hydrocarbons origin, to determine composting rates for nonpolar extractable compounds and to calculate real content of non-polar extractable compounds in final composting status on the assumption that the contamination is of mineral oil type. This is the survey into the results obtained in this field published in the literature as well as reached in our laboratory. (author)

The bacterial catabolism of polycyclic aromatic hydrocarbons: Characterization of three hydratase-aldolase-catalyzed reactions

Directory of Open Access Journals (Sweden)

Jake A. LeVieux

2016-12-01

Full Text Available Polycyclic aromatic hydrocarbons (PAHs are highly toxic, pervasive environmental pollutants with mutagenic, teratogenic, and carcinogenic properties. There is interest in exploiting the nutritional capabilities of microbes to remove PAHs from various environments including those impacted by improper disposal or spills. Although there is a considerable body of literature on PAH degradation, the substrates and products for many of the enzymes have never been identified and many proposed activities have never been confirmed. This is particularly true for high molecular weight PAHs (e.g., phenanthrene, fluoranthene, and pyrene. As a result, pathways for the degradation of these compounds are proposed to follow one elucidated for naphthalene with limited experimental verification. In this pathway, ring fission produces a species that can undergo a non-enzymatic cyclization reaction. An isomerase opens the ring and catalyzes a cis to trans double bond isomerization. The resulting product is the substrate for a hydratase-aldolase, which catalyzes the addition of water to the double bond of an α,β-unsaturated ketone, followed by a retro-aldol cleavage. Initial kinetic and mechanistic studies of the hydratase-aldolase in the naphthalene pathway (designated NahE and two hydratase-aldolases in the phenanthrene pathway (PhdG and PhdJ have been completed. Crystallographic work on two of the enzymes (NahE and PhdJ provides a rudimentary picture of the mechanism and a platform for future work to identify the structural basis for catalysis and the individual specificities of these hydratase-aldolases.

Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

Science.gov (United States)

Greene, Samuel M; Shan, Xiao; Clary, David C

2015-12-17

Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems.

Photo- and radiation chemical studies of intermediates involved in excited-state electron-transfer reactions

International Nuclear Information System (INIS)

Hoffman, M.Z.

1985-01-01

Excited-state inter- and intramolecular electron-transfer reactions lie at the heart of the most photochemical solar energy conversion schemes. The authors research, which has utilized the techniques of continuous and pulsed photolysis and radiolysis, has focused on three general aspects of these reactions involving transition metal coordination complexes and electron donor-acceptor complexes: i) the effect of solution medium on the properties and quenching of the excited states; ii) the control of the quantum yields of formation of redox products; iii) the mechanism by which reduced species interact with water to yield H 2 homogeneously and heterogeneously. EDTA is among the most popular sacrificial electron donors used in model systems. Its role is to scavenge the oxidized form of the photosensitizer in order to prevent its rapid reaction with the reduced form of the electron relay species that results from the electron-transfer quenching of the excited photosensitizer. In systems involving MV 2+ , the radicals resulting from the oxidation of EDTA can eventually lead to the generation of a second equivalent of MV + ; the reducing agent is believed to be a radical localized on the carbon atom alpha to the carboxylate group. The reaction of radiolytically-generated OH/H with EDTA produces this radical directly via H-abstraction or indirectly via deprotonation of the carbon atom adjacent to the nitrogen radical site in the oxidized amine moiety; it reduces MV 2+ with rate constants of 2.8 x 10 9 , 7.6 x 10 9 , and 8.5 x 10 6 M -1 s -1 at pH 12.5, 8.3, and 4.7, respectively. Degradative decarboxylation of EDTA-radicals and their back electron-transfer reactions are enhanced in acidic solution causing the yield of MV + to be severely diminished

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

Directory of Open Access Journals (Sweden)

Ting Ma

2014-04-01

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

New Hydrocarbon Degradation Pathways in the Microbial Metagenome from Brazilian Petroleum Reservoirs

Science.gov (United States)

Sierra-García, Isabel Natalia; Correa Alvarez, Javier; Pantaroto de Vasconcellos, Suzan; Pereira de Souza, Anete; dos Santos Neto, Eugenio Vaz; de Oliveira, Valéria Maia

2014-01-01

Current knowledge of the microbial diversity and metabolic pathways involved in hydrocarbon degradation in petroleum reservoirs is still limited, mostly due to the difficulty in recovering the complex community from such an extreme environment. Metagenomics is a valuable tool to investigate the genetic and functional diversity of previously uncultured microorganisms in natural environments. Using a function-driven metagenomic approach, we investigated the metabolic abilities of microbial communities in oil reservoirs. Here, we describe novel functional metabolic pathways involved in the biodegradation of aromatic compounds in a metagenomic library obtained from an oil reservoir. Although many of the deduced proteins shared homology with known enzymes of different well-described aerobic and anaerobic catabolic pathways, the metagenomic fragments did not contain the complete clusters known to be involved in hydrocarbon degradation. Instead, the metagenomic fragments comprised genes belonging to different pathways, showing novel gene arrangements. These results reinforce the potential of the metagenomic approach for the identification and elucidation of new genes and pathways in poorly studied environments and contribute to a broader perspective on the hydrocarbon degradation processes in petroleum reservoirs. PMID:24587220

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

International Nuclear Information System (INIS)

Swanson, R.

1984-01-01

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

Halogenated hydrocarbons - an environmental problem

Energy Technology Data Exchange (ETDEWEB)

Schoeler, H F; Thofern, E

1984-01-01

The paper provides a survey of the incidence of highly volatile halogenated hydrocarbons in ground, surface and drinking water as well as in the snows of Western Germany. Almost the entire production of chlorinated solvents is released into the environment. The absorption media are mostly soil, water and atmosphere. Whereas in the atmosphere elimination reactions take place, solvents that have passed the soil get into the ground water owing to their persistence and can cause considerable pollutions of drinking water. Moreover haloforms may occur in drinking water, which are produced during chlorine disinfection of pre-treated water.

Studies of Catalytic Properties of Inorganic Rock Matrices in Redox Reactions

Directory of Open Access Journals (Sweden)

Nikolay M. Dobrynkin

2017-09-01

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

Effect of temperature on photochemical smog reactions

Energy Technology Data Exchange (ETDEWEB)

Bufalini, J J; Altshuller, A P

1963-01-01

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

Bioremediation of a Petroleum-Hydrocarbon Polluted Agricultural ...

African Journals Online (AJOL)

A combination of field cells involving a control and five treatment cells were evaluated under field conditions in the bioremediation of a petroleum- hydrocarbon polluted agricultural soil over a six-week period. Previous works have indicated that crude oil contamination of soils depletes oxygen reserves in the soils and slows ...

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

International Nuclear Information System (INIS)

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

1991-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1991-07-01

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

Surfactant-enhanced recovery of dissolved hydrocarbons at petroleum production facilities

International Nuclear Information System (INIS)

Freeman, J.T.; Mayes, M.; Wassmuth, F.; Taylor, K.; Rae, W.; Kuipers, F.

1997-01-01

The feasibility and cost effectiveness of surfactant-enhanced pumping to reduce source concentrations of petroleum hydrocarbons from contaminated soils was discussed. Light non-aqueous phase liquids (LNAPL) hydrocarbons are present beneath many petroleum production processing facilities in western Canada. Complete removal of LNAPLs from geologic materials is difficult and expensive. Treatment technologies include costly ex-situ methods such as excavation and in-situ methods such as physical extraction by soil venting and pumping, bioremediation, and combination methods such as bioventing, bioslurping or air sparging. Surfactant-aided pumping can reduce source hydrocarbon concentrations when used in conjunction with traditional pump and treat, or deep well injection. This study involved the selection of an appropriate surfactant from a wide variety of commercially available products. A site contaminated by hydrocarbons in Turner Valley, Alberta, was used for field scale testing. One of the major problems was quantifying the increase in the dissolved hydrocarbon concentrations in the recovered water once a surfactant was added. From the 30 surfactants screened in a series of washing and oil solubilization tests, two surfactants, Brij 97 and Tween 80, were selected for further evaluation. Increased hydrocarbon recovery was observed within 10 days of the introduction of the first surfactant. 2 refs., 7 figs

Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes

International Nuclear Information System (INIS)

Frenklach, M.; Feigelson, E.D.

1989-01-01

Production of polycyclic aromatic hydrocarbons in carbon-rich circumstellar envelopes was investigated using a kinetic approach. A detailed chemical reaction mechanism of gas-phase PAH formation and growth, containing approximately 100 reactions of 40 species, was numerically solved under the physical conditions expected in cool stellar winds. The chemistry is based on studies of soot production in hydrocarbon pyrolysis and combustion. Several first-ring and second-ring cyclization processes were considered. A linear lumping algorithm was used to describe PAH growth beyond the second aromatic ring. PAH production using this mechanism was examined with respect to a grid of idealized constant velocity stellar winds as well as several published astrophysical models. The basic result is that the onset of PAH production in the interstellar envelopes is predicted to occur within the temperature interval of 1100 to 900 K. The absolute amounts of the PAHs formed, however, are very sensitive to a number of parameters, both chemical and astrophysical, whose values are not accurately known. Astrophysically meaningful quantities of PAHs require particularly dense and slow stellar winds and high initial acetylene abundance. It is suggested that most of the PAHs may be produced in a relatively small fraction of carbon-rich red giants. 87 refs

Characterization of bacterial community structure in a hydrocarbon-contaminated tropical African soil.

Science.gov (United States)

Salam, Lateef B; Ilori, Mathew O; Amund, Olukayode O; LiiMien, Yee; Nojiri, Hideaki

2018-04-01

The bacterial community structure in a hydrocarbon-contaminated Mechanical Engineering Workshop (MWO) soil was deciphered using 16S rRNA gene clone library analysis. Four hundred and thirty-seven clones cutting across 13 bacterial phyla were recovered from the soil. The representative bacterial phyla identified from MWO soil are Proteobacteria, Bacteroidetes, Chloroflexi, Acidobacteria, Firmicutes, Actinobacteria, Verrucomicrobia, Planctomycetes, Ignavibacteriae, Spirochaetes, Chlamydiae, Candidatus Saccharibacteria and Parcubacteria. Proteobacteria is preponderant in the contaminated soil (51.2%) with all classes except Epsilonproteobacteria duly represented. Rarefaction analysis indicates 42%, 52% and 77% of the clone library is covered at the species, genus and family/class delineations with Shannon diversity (H') and Chao1 richness indices of 5.59 and 1126, respectively. A sizeable number of bacterial phylotypes in the clone library shared high similarities with strains previously described to be involved in hydrocarbon biodegradation. Novel uncultured genera were identified that have not been previously reported from tropical African soil to be associated with natural attenuation of hydrocarbon pollutants. This study establishes the involvement of a wide array of physiologically diverse bacterial groups in natural attenuation of hydrocarbon pollutants in soil.

MICROBIAL CELL-SURFACE HYDROPHOBICITY - THE INVOLVEMENT OF ELECTROSTATIC INTERACTIONS IN MICROBIAL ADHESION TO HYDROCARBONS (MATH)

NARCIS (Netherlands)

GEERTSEMADOORNBUSCH, GI; VANDERMEI, HC; BUSSCHER, HJ

Microbial adhesion to hydrocarbons (MATH) is the most commonly used method to determine microbial cell surface hydrophobicity. Since, however, the assay is based on adhesion, it is questionable whether the results reflect only the cell surface hydrophobicity or an interplay of hydrophobicity and

A Hierarchy of Homodesmotic Reactions for Thermochemistry

Science.gov (United States)

Schleyer, Paul v. R.

2009-01-01

Chemical equations that balance bond types and atom hybridization to different degrees are often used in computational thermochemistry, for example, to increase accuracy when lower levels of theory are employed. We expose the widespread confusion over such classes of equations and demonstrate that the two most widely used definitions of “homodesmotic” reactions are not equivalent. New definitions are introduced and a consistent hierarchy of reaction classes (RC1 – RC5) for hydrocarbons is constructed: isogyric (RC1) ⊇ isodesmic (RC2) ⊇ hypohomodesmotic (RC3) ⊇ homodesmotic (RC4) ⊇ hyperhomodesmotic (RC5). Each of these successively conserves larger molecular fragments. The concept of isodesmic bond separation reactions is generalized to all classes in this hierarchy, providing a unique sectioning of a given molecule for each reaction type. Several ab initio and density functional methods are applied to the bond separation reactions of 38 hydrocarbons containing five or six carbon atoms. RC4 and RC5 reactions provide bond separation enthalpies with errors consistently less than 0.4 kcal mol−1 across a wide range of theoretical levels, performing significantly better than the other reaction types and far superior to atomization routes. Our recommended bond separation reactions were demonstrated by determining the enthalpies of formation (at 298 K) of 1,3,5-hexatriyne (163.7 ± 0.4 kcal mol−1), 1,3,5,7-octatetrayne (217.6 ± 0.6 kcal mol−1), the larger polyynes C10H2 through C26H2, and an infinite acetylenic carbon chain. PMID:19182999

Suitability of the hydrocarbon-hydroxylating molybdenum-enzyme ethylbenzene dehydrogenase for industrial chiral alcohol production.

Science.gov (United States)

Tataruch, M; Heider, J; Bryjak, J; Nowak, P; Knack, D; Czerniak, A; Liesiene, J; Szaleniec, M

2014-12-20

The molybdenum/iron-sulfur/heme protein ethylbenzene dehydrogenase (EbDH) was successfully applied to catalyze enantiospecific hydroxylation of alkylaromatic and alkylheterocyclic compounds. The optimization of the synthetic procedure involves use of the enzyme in a crude purification state that saves significant preparation effort and is more stable than purified EbDH without exhibiting unwanted side reactions. Moreover, immobilization of the enzyme on a crystalline cellulose support and changes in reaction conditions were introduced in order to increase the amounts of product formed (anaerobic atmosphere, electrochemical electron acceptor recycling or utilization of ferricyanide as alternative electron acceptor in high concentrations). We report here on an extension of effective enzyme activity from 4h to more than 10 days and final product yields of up to 0.4-0.5g/l, which represent a decent starting point for further optimization. Therefore, we expect that the hydrocarbon-hydroxylation capabilities of EbDH may be developed into a new process of industrial production of chiral alcohols. Copyright © 2014 Elsevier B.V. All rights reserved.

Study of the main parameters involved in carbothermal reduction reaction of silica aiming to obtain silicon nitride powder

International Nuclear Information System (INIS)

Rocha, J.C. da; Greca, M.C.

1989-01-01

The influence of main parameters involved in the method of silicon nitride attainment by carbothermal reduction of silica followed by nitridation were studied in isothermal experiments of fine powder mixtures of silica and graphite in a nitrogen gas flow. The time, temperature, rate C/SiO 2 and flow of nitrogen were varied since they are the main parameters involved in this kind of reaction. The products of reaction were analysed by X-ray diffraction to identify the crystalline phases and as a result was obtained the nucleation of silicon nitride phase. Meanwhile, corroborating prior results, we verified to be difficult the progress of the reaction and the inhibition of formation of silicon carbide phase, the last one being associated to the formation of silicon nitride phase due to thermodynamic matters [pt

Distribution of hydrocarbon-utilizing microorganisms and hydrocarbon biodegradation potentials in Alaskan continental shelf areas

International Nuclear Information System (INIS)

Roubal, G.; Atlas, R.M.

1978-01-01

Hydrocarbon-utilizing microogranisms were enumerated from Alaskan continental shelf areas by using plate counts and a new most-probable-number procedure based on mineralization of 14 C-labeled hydrocarbons. Hydrocarbon utilizers were ubiquitously distributed, with no significant overall concentration differences between sampling regions or between surface water and sediment samples. There were, however, significant seasonal differences in numbers of hydrocarbon utilizers. Distribution of hydrocarbon utilizers within Cook Inlet was positively correlated with occurrence of hydrocarbons in the environment. Hydrocarbon biodegradation potentials were measured by using 14 C-radiolabeled hydrocarbon-spiked crude oil. There was no significant correlation between numbers of hydrocarbon utilizers and hydrocarbon biodegradation potentials. The biodegradation potentials showed large seasonal variations in the Beaufort Sea, probably due to seasonal depletion of available nutrients. Non-nutrient-limited biodegradation potentials followed the order hexadecane > naphthalene >> pristane > benzanthracene. In Cook Inlet, biodegradation potentials for hexadecane and naphthalene were dependent on availability of inorganic nutrients. Biodegradation potentials for pristane and benzanthracene were restricted, probably by resistance to attack by available enzymes in the indigenous population

Aryl hydrocarbon receptor overexpression in miniaturized follicles in female pattern hair loss.

Science.gov (United States)

Ramos, Paulo Müller; Brianezi, Gabrielli; Martins, Ana Carolina Pereira; Silva, Márcia Guimarães da; Marques, Mariângela Esther Alencar; Miot, Hélio Amante

2017-01-01

The etiopathogenesis of female pattern hair loss is still poorly understood. In addition to genetic and hormonal elements, environmental factors could be involved. The aryl hydrocarbon receptor is expressed in keratinocytes and can be activated by environmental pollutants leading to alterations in the cell cycle, inflammation, and apoptosis. Here we demonstrate the overexpression of nuclear aryl hydrocarbon receptors in miniaturized hair follicles in female pattern hair loss.

Conversion of Methane to C2 Hydrocarbons and Hydrogen Using a Gliding Arc Reactor

International Nuclear Information System (INIS)

Hu Shuanghui; Wang Baowei; Lv Yijun; Yan Wenjuan

2013-01-01

Methane conversion has been studied using gliding arc plasma in the presence of argon. The process was conducted at atmospheric pressure and ambient temperature. The focus of this research was to develop a process of converting methane to C 2 hydrocarbons and hydrogen. The main parameters, including the CH 4 /Ar mole ratio, the CH 4 flow rate, the input voltage, and the minimum electrode gap, were varied to investigate their effects on methane conversion rate, product distribution, energy consumption, carbon deposit, and reaction stability. The specific energy requirement (SER) was used to express the energy utilization efficiency of the process and provided a practical guidance for optimizing reaction conditions for improving energy efficiency. It was found that the carbon deposition was not conducive to methane conversion, and the gliding arc plasma discharge reached a stable state twelve minutes later. Optimum conditions for methane conversion were suggested. The maximum methane conversion rate of 43.39% was obtained under the optimum conditions. Also, C 2 hydrocarbons selectivity, C 2 hydrocarbons yield, H 2 selectivity, H 2 yield and SER were 87.20%, 37.83%, 81.28%, 35.27%, and 2.09 MJ/mol, respectively.

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min Suk

2017-02-16

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured to be submerged in the liquid. The plasma plume from the plasma torch can cause reformation of the hydrocarbon. The device can use a variety of plasma torches that can be arranged in a variety of positions in the liquid container. The devices can be used for the reformation of gaseous hydrocarbons and/or liquid hydrocarbons. The reformation can produce methane, lower hydrocarbons, higher hydrocarbons, hydrogen gas, water, carbon dioxide, carbon monoxide, or a combination thereof.

Investigation of large α production in reactions involving weakly bound 7Li

Science.gov (United States)

Pandit, S. K.; Shrivastava, A.; Mahata, K.; Parkar, V. V.; Palit, R.; Keeley, N.; Rout, P. C.; Kumar, A.; Ramachandran, K.; Bhattacharyya, S.; Nanal, V.; Palshetkar, C. S.; Nag, T. N.; Gupta, Shilpi; Biswas, S.; Saha, S.; Sethi, J.; Singh, P.; Chatterjee, A.; Kailas, S.

2017-10-01

The origin of the large α -particle production cross sections in systems involving weakly bound 7Li projectiles has been investigated by measuring the cross sections of all possible fragment-capture as well as complete fusion using the particle-γ coincidence, in-beam, and off-beam γ -ray counting techniques for the 7Li+93Nb system at near Coulomb barrier energies. Almost all of the inclusive α -particle yield has been accounted for. While the t -capture mechanism is found to be dominant (˜70 % ), compound nuclear evaporation and breakup processes contribute ˜15 % each to the inclusive α -particle production in the measured energy range. Systematic behavior of the t capture and inclusive α cross sections for reactions involving 7Li over a wide mass range is also reported.

Metabolic activation of polycyclic and heterocyclic aromatic hydrocarbons and DNA damage: A review

International Nuclear Information System (INIS)

Xue Weiling; Warshawsky, David

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic compounds (HACs) constitute a major class of chemical carcinogens present in the environment. These compounds require activation to electrophilic metabolites to exert their mutagenic or carcinogenic effects. There are three principal pathways currently proposed for metabolic activation of PAH and HAC: the pathway via bay region dihydrodiol epoxide by cytochrome P450 enzymes (CYPs), the pathway via radical cation by one-electron oxidation, and the ortho-quinone pathway by dihydrodiol dehydrogenase (DD). In addition to these major pathways, a brief description of a minor metabolic activation pathway, sulfonation, for PAHs that contain a primary benzylic alcoholic group or secondary hydroxyl group(s) is included in this review. The DNA damages caused through the reactive metabolites of PAH/HAC are described involving the DNA covalent binding to form stable or depurinating adducts, the formation of apurinic sites, and the oxidative damage. The review emphasizes the chemical/biochemical reactions involved in the metabolic processes and the chemical structures of metabolites and DNA adducts

Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms

Energy Technology Data Exchange (ETDEWEB)

Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas [Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena, Helmholtzweg 3, D-07743 Jena (Germany)

2017-02-10

A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

Petroleum hydrocarbons

International Nuclear Information System (INIS)

Farrington, J.W.; Teal, J.M.; Parker, P.L.

1976-01-01

Methods for analysis of petroleum hydrocarbons in marine samples are presented. Types of hydrocarbons present and their origins are discussed. Principles and methods of analysis are outlined. Infrared spectrometry, uv spectrometry, gas chromatography, mass spectroscopy, and carbon 14 measurements are described

The rate of the reaction between C2H and C2H2 at interstellar temperatures

Science.gov (United States)

Herbst, E.; Woon, D. E.

1997-01-01

The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

Low energy ion-molecule reactions

International Nuclear Information System (INIS)

Farrar, J.M.

1986-01-01

The authors work during the past year has focused on several problems in the condensation reactions of C + and CH 3 + with small molecules, particularly hydrocarbons. Their emphasis has been on understanding the dynamics of collision complex formation and isomerization of transient intermediates along the reaction coordinate. In many ionic reactions, intermediates having non-classical valence structures may be nearly as stable as their classical analogs, in contrast with neutral systems where the non-classical structures are much less stable. The C + + NH 3 system shows this behavior, indicating that the non-classical HCNH 2 + structure formed by insertion of C + into the N-H bond serves as a precursor to the products. N-H bond cleavage in this intermediate to form HCNH + occurs over a large barrier and occurs more readily than the 1,2 hydrogen atom shift to form the classical H 2 C = NH + intermediate. Their experimental kinetic energy distribution for this channel is consistent with the presence of a large exit channel barrier. Their recently published work on C + + H 2 O also demonstrates this phenomenon. The CHOH + hydroxycarbene cation serves as the initial intermediate and isomerization to the classical H 2 CO + cation is competitive with O-H or C-H cleavage to yield the formyl, HCO + , or isoformyl, COH + , cations. They have also completed studies on the reactions of C + with O 2 , CH 3 OH, HCN, and the two-carbon containing hydrocarbons ethane, ethylene, and acetylene

Converting high boiling hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Terrisse, H; DuFour, L

1929-02-12

A process is given for converting high boiling hydrocarbons into low boiling hydrocarbons, characterized in that the high boiling hydrocarbons are heated to 200 to 500/sup 0/C in the presence of ferrous chloride and of such gases as hydrogen, water gas, and the like gases under a pressure of from 5 to 40 kilograms per square centimeter. The desulfurization of the hydrocarbons occurs simultaneously.

Hydrocarbons conversions over mineral ion-exchangers used in uranium ore waste treatment

International Nuclear Information System (INIS)

Azzouz, A.

1988-05-01

Preliminary experiments were carried out in order to investigate catalytic activities in hydrocarbons reactions of natural and synthetic zeolites previously loaded with heavy elements as lanthanides and actinides in yellow cake treatment. This way could be considered as an interesting low coast alternative in revalorifying these mineral ion-exchangers. (author)

Advances in heterocycle synthesis via [3+m]-cycloaddition reactions involving an azaoxyallyl cation as the key intermediate.

Science.gov (United States)

Xuan, Jun; Cao, Xia; Cheng, Xiao

2018-05-17

Heterocyclic compounds are widely found in many natural isolates and medicinally relevant compounds, as well as some fine chemicals. The development of general and efficient methods for the construction of heterocyclic compounds is one of the most important tasks in synthetic organic chemistry. Along these lines, [3+m]-cycloaddition reactions involving in situ generated azaoxyallyl cations as the 3-atom units have emerged as a powerful method for the synthesis of nitrogen-containing heterocycles. In this feature article, we highlight recent advances in this rapidly growing area, mainly focusing on the reaction design as well as the reaction mechanism.

Do sealless pumps belong in hydrocarbon processing services?

Energy Technology Data Exchange (ETDEWEB)

Bennett, Shawn L. [Sundyne Corporation, Arvada, CO (Brazil)

2004-07-01

Sealless pump technology seems unimaginable in the hot, dirty and high-pressure world of hydrocarbon processing. Furthermore the high flow rates typical of the industry seem incompatible with sealless pumps. Seals and their environmental controls used in conventional technologies are not immune from these factors making sealless worth another look. In October 2000 the Sealless Centrifugal Pump Specification API 685 was published. This specification lends sealless pumps credibility and emphasizes the proper application of the technology. In many process units seal leaks can be extremely dangerous and costly. The heavy hydrocarbons can auto-ignite and light hydrocarbons will tend to find a source of ignition. The ever-increasing requirements for clean fuels are driving many of the current refinery upgrades. Best Also available control technology requirements and additional focus on Environmental Health and Safety increase the attractiveness of sealless technology to mitigate the hazards associated with seal leaks. Sealless has a place in hydrocarbon processing to eliminate seals, provide mechanical simplification, and ensure personnel/environmental protection. The proper application involves evaluating canned motor/magnetic drive technology, API 685 Guidelines, and vapor pressure versus pump circuit pressure analysis. There are four (4) specific processes where sealless pumps should be targeted: Alkylation, Sulfur Recovery/Hydrotreating, Naphtha Reforming Production, and Neutralization. (author)

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

International Nuclear Information System (INIS)

1985-01-01

Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

Biodegradation and chemical characterization of petroleum diesel hydrocarbons in seawater at low temperatures

OpenAIRE

Bausch, Alexandre Renee

2010-01-01

Master's thesis in Environmental engineering Petroleum hydrocarbons are a major source of marine contamination. Biodegradation, which is fundamental for the natural attenuation of these hydrocarbons in nature, involves mineralization or transformation of organic compounds by autochthonous microorganism communities. Various limiting factors characteristic of the petroleum, the external environment, and the microbial community determine the fate of oil (e.g., diesel) in the marine environmen...

Crystal-plane effects of MFI zeolite in catalytic conversion of methanol to hydrocarbons

KAUST Repository

Wang, Ning; Sun, Wenjing; Hou, Yilin; Ge, Binghui; Hu, Ling; Nie, Jingqi; Qian, Weizhong; Wei, Fei

2018-01-01

We report the direct characterization of coke information in the clearly resolved (0 1 0) and (1 0 0) planes of various anisotropic MFI zeolites using EELS techniques, in a model reaction of methanol to hydrocarbons. For the first time, we found

Composite catalyst for carbon monoxide and hydrocarbon oxidation

Science.gov (United States)

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

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

A computational study of ethylene–air sooting flames: Effects of large polycyclic aromatic hydrocarbons

KAUST Repository

Selvaraj, Prabhu; Arias, Paul G.; Lee, Bok Jik; Im, Hong G.; Wang, Yu; Gao, Yang; Park, Sungwoo; Sarathy, Mani; Lu, Tianfeng; Chung, Suk-Ho

2015-01-01

formation to various chemical pathways for large polycyclic aromatic hydrocarbons (PAH). The gas-phase chemical mechanism adopted the KAUST-Aramco PAH Mech 1.0, which utilized the AramcoMech 1.3 for gas-phase reactions validated for up to C2 fuels

A method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Fakhriev, A.M.; Galiautdinov, N.G.; Kashevarov, L.A.; Mazgarov, A.M.

1982-01-01

The method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons, which involves extracting hydrocarbons using a dimethylsulfoxide extractant, is improved by using a dimethylsulfoxide blend and 10-60 percent (by volume) diethylenetriamine or polyethylenepolyamine which contains diethylenetriamine, triethylenetetramine and tetraethylenepentamine, in order to eliminate the above compounds. Polyethylenepolyamine is produced as a by-product during the production of ethylenediamine. Elimination is performed at 0-50 degrees and 1-60 atmospheres of pressure. Here, the extractant may contain up to 10 percent water. The use of the proposed method, rather than the existing method, will make it possible to increase hydrocarbon elimination from mercaptans by 40 percent and from H/sub 2/S by 10 percent when the same amount is eliminated from dialkylsulfides.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

Science.gov (United States)

De, Sudipta; Saha, Basudeb; Luque, Rafael

2015-02-01

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photo-assisted removal of fuel oil hydrocarbons from wood and concrete.

Science.gov (United States)

Popova, Inna E; Kozliak, Evguenii I

2008-08-01

A novel photo-treatment to decontaminate building structural elements polluted with fuel oil hydrocarbons as a result of spillage and/or a catastrophic flood was examined. A proof-of-concept study evaluating the photocatalytic removal of hydrocarbons (n-hexadecane and fuel oil #2) from contaminated wood (southern yellow pine) and concrete was conducted using scintillation counting (with (14)C-labeled n-hexadecane) and gas chromatography. Contaminated samples were irradiated by UV or fluorescent light in the absence or presence of a photocatalyst, TiO(2). As a result of the treatment, under various scenarios, up to 80-98% of the originally applied n-hexadecane was removed, within a wide range of contaminant concentrations (4-250 mg/g wood). The essential treatment time increased from 1-7 days for low concentrations to several weeks for high concentrations. Mass balance experiments showed that the only product formed from (14)C-labeled n-hexadecane in detectable amounts was (14)CO(2). For low amounts of applied hydrocarbon (4-20 mg/g wood), the overall process rate was limited by the contaminant transport/mobility whereas for high n-hexadecane concentrations (150-250 mg/g, corresponding to 50-80% filling of wood pores), the key factor was the photochemical reaction. Photodegradation experiments conducted with standard heating fuel oil #2 (a representative real-world contaminant) resulted in a significant (up to 80%) photochemical removal of mid-size hydrocarbons (C(13)-C(17)) in 3 weeks whereas heavier hydrocarbons (> C(17)) were not affected; light hydrocarbons (evaporation. These results point toward a promising technique to reclaim wooden and concrete structures contaminated with semi-volatile chemicals.

Minimum Energy Pathways for Chemical Reactions

Science.gov (United States)

Walch, S. P.; Langhoff, S. R. (Technical Monitor)

1995-01-01

Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

Mechanistic aspects of ionic reactions in flames

DEFF Research Database (Denmark)

Egsgaard, H.; Carlsen, L.

1993-01-01

Some fundamentals of the ion chemistry of flames are summarized. Mechanistic aspects of ionic reactions in flames have been studied using a VG PlasmaQuad, the ICP-system being substituted by a simple quartz burner. Simple hydrocarbon flames as well as sulfur-containing flames have been investigated...

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...

Laboratory analytical methods for the determination of the hydrocarbon status of soils (a review)

Science.gov (United States)

Pikovskii, Yu. I.; Korotkov, L. A.; Smirnova, M. A.; Kovach, R. G.

2017-10-01

Laboratory analytical methods suitable for the determination of the hydrocarbon status of soils (a specific soil characteristic involving information on the total content and qualitative features of soluble (bitumoid) carbonaceous substances and individual hydrocarbons (polycyclic aromatic hydrocarbons, alkanes, etc.) in bitumoid, as well as the composition and content of hydrocarbon gases) have been considered. Among different physicochemical methods of study, attention is focused on the methods suitable for the wide use. Luminescence-bituminological analysis, low-temperature spectrofluorimetry (Shpolskii spectroscopy), infrared (IR) spectroscopy, gas chromatography, chromatography-mass spectrometry, and some other methods have been characterized, as well as sample preparation features. Advantages and limitations of each of these methods are described; their efficiency, instrumental complexity, analysis duration, and accuracy are assessed.

Performance of a Throttle Cycle Refrigerator with Nitrogen-Hydrocarbon and Argon-Hydrocarbon Mixtures

Science.gov (United States)

Venkatarathnam, G.; Senthil Kumar, P.; Srinivasa Murthy, S.

2004-06-01

Throttle cycle refrigerators are a class of vapor compression refrigerators that can provide refrigeration at cryogenic temperatures and operate with refrigerant mixtures. The performance of our prototype refrigerators with nitrogen-hydrocarbon, nitrogen-hydrocarbon-helium and argon-hydrocarbon refrigerant mixtures is presented in this paper.

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in Hong Kong marine sediments

International Nuclear Information System (INIS)

Zheng, G.J.; Richardson, B.J.

1999-01-01

A total of 20 surficial sediment samples, obtained from Hong Kong coastal waters, were analysed for petroleum hydrocarbons (PHCs) and a suite of 15 polycyclic aromatic hydrocarbons (PAHs). The results indicate that Hong Kong coastal sediments are often seriously polluted with petroleum related hydrocarbons. This is especially so in heavily urbanised or industrialized localities, such as Kowloon Bay (Victoria Harbour), Tsing Yi North and Tolo Harbour. Petroleum hydrocarbon pollutants in marine sediments are believed to be mainly derived from the transportation of oil, shipping activities, spillages, and industrial, stormwater and waste wastewater discharge. The ratio of unresolved complex mixture (UCM) to n-alkanes, carbon preference index (CPI), and n-C 16 values indicate that the main contribution to petroleum hydrocarbon contamination is via oil and its products. Pollutant sources appear to be stable and continuing when compared with previous data. (author)

Purifying hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Demoulins, H D; Garner, F H

1923-02-07

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

Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

International Nuclear Information System (INIS)

Fagerstroem, K.

1993-01-01

The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

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

International Nuclear Information System (INIS)

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

1979-01-01

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

Collisions of polyatomic ions with surfaces: incident energy partitioning and chemical reactions

International Nuclear Information System (INIS)

Zabka, J.; Roithova, J.; Dolejsek, Z.; Herman, Z.

2002-01-01

Collision of polyatomic ions with surfaces were investigated in ion-surface scattering experiments to obtain more information on energy partitioning in ion-surface collision and on chemical reactions at surfaces. Mass spectra, translation energy and angular distributions of product ions were measured in dependence on the incident energy and the incident angle of polyatomic projectiles. From these data distributions of energy fractions resulting in internal excitation of the projectile, translation energy of the product ions, and energy absorbed by the surface were determined. The surface investigated were a standard stainless steel surface, covered by hydrocarbons, carbon surfaces at room and elevated temperatures, and several surfaces covered by a self-assembled monolayers (C 12 -hydrocarbon SAM, C 11 -perfluorohydrocarbon SAM, and C 11 hydrocarbon with terminal -COOH group SAM). The main processes observed at collision energies of 10 - 50 eV were: neutralization of the ions at surfaces, inelastic scattering and dissociations of the projectile ions, quasi elastic scattering of the projectile ions, and chemical reactions with the surface material (usually hydrogen-atom transfer reactions). The ion survival factor was estimated to be a few percent for even-electron ions (like protonated ethanol ion, C 2 H 5 O + , CD 5 + ) and about 10 - 10 2 times lower for radical ions (like ethanol and benzene molecular ions, CD 4 + ). In the polyatomic ion -surface energy transfer experiments, the ethanol molecular ion was used as a well-characterized projectile ion. The results with most of the surfaces studied showed in the collision energy range of 13 - 32 eV that most collisions were strongly inelastic with about 6 - 8 % of the incident projectile energy transformed into internal excitation of the projectile (independent of the incident angle) and led partially to its further dissociation in a unimolecular way after the interaction with the surface. The incident energy

Exploration of hydrocarbon degrading bacteria on soils contaminated by crude oil from South Sumatera

Directory of Open Access Journals (Sweden)

A. Napoleon

2014-07-01

Full Text Available The goal of this research was to explore hydrocarbon degrading bacteria on crude oil contaminated soil with potential to degrade hydrocarbon in oil pollutant. The research started by early August 2013 till January 2014. Soil sampling for this research was taken on several places with contaminated soil location such as Benakat, Rimau, and Pengabuan all of it located in South Sumatera. Conclusion from this research Isolates obtained from three (3 sites of contaminated soil and treated using SBS medium were Bacillus cereus, Pseudomonas aeruginosa, Klebsiella pnumoniae, Streptococcus beta hemolisa, Proteus mirabilis, Staphylococcus epidermis and Acinotobacter calcoaceticus. Isolates that survived on 300 ppm of hydrocarbon concentration were Bacillus cereus, Pseudomonas aeruginosa and Acinetobacter cakciaceticus Selected isolates posses the ability to degrade hydrocarbon by breaking hydrocarbon substance as the energy source to support isolates existence up to 1,67 TPH level. Based on results accomplish by this research, we urge for further research involving the capacity of isolates to degrade wide variety of hydrocarbon substance and more to develop the potential of these bacteria for bioremediation.

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

Science.gov (United States)

Guo, H; Lee, S C; Louie, P K K; Ho, K F

2004-12-01

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

International Nuclear Information System (INIS)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

2017-01-01

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

2017-11-14

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

Pore-scale studies of multiphase flow and reaction involving CO2 sequestration in geologic formations

Science.gov (United States)

Kang, Q.; Wang, M.; Lichtner, P. C.

2008-12-01

In geologic CO2 sequestration, pore-scale interfacial phenomena ultimately govern the key processes of fluid mobility, chemical transport, adsorption, and reaction. However, spatial heterogeneity at the pore scale cannot be resolved at the continuum scale, where averaging occurs over length scales much larger than typical pore sizes. Natural porous media, such as sedimentary rocks and other geological media encountered in subsurface formations, are inherently heterogeneous. This pore-scale heterogeneity can produce variabilities in flow, transport, and reaction processes that take place within a porous medium, and can result in spatial variations in fluid velocity, aqueous concentrations, and reaction rates. Consequently, the unresolved spatial heterogeneity at the pore scale may be important for reactive transport modeling at the larger scale. In addition, current continuum models of surface complexation reactions ignore a fundamental property of physical systems, namely conservation of charge. Therefore, to better understand multiphase flow and reaction involving CO2 sequestration in geologic formations, it is necessary to quantitatively investigate the influence of the pore-scale heterogeneity on the emergent behavior at the field scale. We have applied the lattice Boltzmann method to simulating the injection of CO2 saturated brine or supercritical CO2 into geological formations at the pore scale. Multiple pore-scale processes, including advection, diffusion, homogeneous reactions among multiple aqueous species, heterogeneous reactions between the aqueous solution and minerals, ion exchange and surface complexation, as well as changes in solid and pore geometry are all taken into account. The rich pore scale information will provide a basis for upscaling to the continuum scale.

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-10-15

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

A review of catalytic aqueous-phase reforming of oxygenated hydrocarbons derived from biorefinery water fractions

NARCIS (Netherlands)

Coronado, I.; Stekrova, M.; Reinikainen, M.; Simell, P.; Lefferts, Leonardus; Lehtonen, J.

2016-01-01

Aqueous-phase reforming (APR) of oxygenated hydrocarbons is a process for the production of hydrogen and light alkanes. The reactants of APR remain in liquid phase during the reaction avoiding an energetically demanding vaporization-step compared to processes such as steam reforming (SR).

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

Energy Technology Data Exchange (ETDEWEB)

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

1979-03-01

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

In vitro toxicity of polycyclic aromatic hydrocarbons and halogenated aromatic hydrocarbons to cetacean cells and tissues

Energy Technology Data Exchange (ETDEWEB)

Carvan, M.J. III.

1993-01-01

Cetaceans bioaccumulate high aromatic hydrocarbon tissue residues, and elevated levels of PCB residues in tissues are proposed to have occurred concurrently with recent epizootic deaths of dolphins. The objectives of this study were: (1) to develop and characterize an epithelial cell line derived from dolphin tissues, (2) to investigate the effects of hydrocarbon pollutants on those cells, and (3) to analyze the toxicity of hydrocarbon pollutants on cetacean tissues in vitro. An epithelial cell line, Carvan dolphin kidney (CDK), isolated from a spontaneously aborted female bottlenose dolphin, Tursiops truncatus, grew rapidly. These cells were neither transformed nor immortal. Velocity sedimentation analysis showed CDK cells contained nuclear aryl hydrocarbon receptor, suggestive of cytochrome P450 inducibility. BaP inhibited mitosis in CDK cells in a dose-dependent manner. Data indicate that CDK cells metabolize BaP, that BaP metabolites bind to cellular DNA initiating unscheduled DNA synthesis, and that the inhibition of cytochrome P450 metabolism decrease the BaP-associated inhibition of mitosis in dolphin cells. The data also suggest that TCDD acts synergistically to increase the levels of DNA damage by the procarcinogen BaP. Cetacean liver microsomes was isolated and evaluated for the presence of cytochrome P450 proteins by SDS-PAGE, apparent minimum molecular weight determination, and immunoblot analysis. P450 activity was induced in cetacean tissue samples and CDK cells by exposure in vitro to one of several cytochrome P450-inducing chemicals. The data suggest that cetacean tissues and cells can be utilized to study the in vitro induction of cytochrome P450, resultant metabolism of xenobiotic contaminants, and the subsequent cellular and molecular responses. However, the identity of specific P450 isozymes involved in this process will remain undetermined until monoclonal antibodies that recognize cetacean P450s can be generated.

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

Science.gov (United States)

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

2009-02-01

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

TYPES OF FI SCAL REGIME IN HYDROCARBON EXPLORATION AND PRODUCTION

Directory of Open Access Journals (Sweden)

Daria Karasalihović-Sedlar

2017-01-01

Full Text Available The choice of the right fi scal regime represents the main object of the energy policy concerning hydrocarbon exploration and production for the state government. For the operator and service companies it represents the terms and conditions for practical conducting of the process in whole. This paper analyse aspects of agreements used in the petroleum indus-try. Elements of agreement, regardless of regime, have been described together with their advantages and disadvantages. Due to the fact that the fi scal regime has to be chosen to attract companies willing to invest in exploration and produc-tion, it represents a relevant part of the business strategy and also a base for the decision making process during start up. It has to minimize the risk for the both parties involved and maximize the state’s share during the exploitation phase. For the companies, it has to be attractive enough to balance risks during the exploration phase with profi ts gained during the exploitation phase. The aim of this paper is to show the existing fi scal systems in the petroleum industry and to analyze the process for concluding a contract regarding the exploration and production of hydrocarbons. An overview of diff er-ent business practices in the oil and gas industry with a detailed breakdown of the contract terms between the parties involved have been described in the paper. The aim of this paper is to show the diff erent possibilities of fi nancial regimes which could help during the negotiation process for conducting hydrocarbon exploration and production for everyone involved.

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min

2017-01-01

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured

Hydrocarbon exploration

Energy Technology Data Exchange (ETDEWEB)

Lerche, I. (South Carolina Univ., Columbia, SC (United States). Dept. of Geological Sciences)

1993-01-01

This special issue of the journal examines various aspects of the on-going search for hydrocarbons, ranging from frontier basins where little data are available, to more mature areas where considerable data are available. The incentives underlying the search for oil are roughly: the social, economic and industrial needs of a nation; the incentive of a corporation to be profitable; and the personal incentives of individuals in the oil industry and governments, which range from financial wealth to power and which are as diverse as the individuals who are involved. From a geopolitical perspective, the needs, requirements, goals, strategies, and philosophies of nations, and groups of nations, also impact on the oil exploration game. Strategies that have been employed have ranged from boycott to austerity and rationing, to physical intervention, to global ''flooding'' with oil by over-production. (author)

Reactions of charged and neutral recoil particles following nuclear transformations. Progress report No. 13

International Nuclear Information System (INIS)

Ache, H.J.

1979-09-01

Research is reported on: caging and solvent effects in hot 38 Cl substitution reactions in chlorinated hydrocarbons (dichlorobenzene), excitation labelling of organic compounds using 80 Br, reactions of energetic tritium with graphite and SiC surfaces, and micellar systems and microemulsions studied by positron annihilation

Oral frostbite injury from intentional abuse of a fluorinated hydrocarbon.

Science.gov (United States)

Kuspis, D A; Krenzelok, E P

1999-01-01

A serious but rarely reported complication of halogenated hydrocarbon inhalation abuse is severe mucosal frostbite. A 16-year-old male attempted to "get high" by inhaling airbrush propellant which contained 1,1-difluoroethane (CAS #75-376). The patient lost consciousness and upon awakening his lips and tongue were frozen. He suffered first- and second-degree burns of the larynx with vocal cord involvement and first-degree burns of the trachea, main stem bronchi, and esophagus. The oral cavity had second- and third-degree burns which required debridement. This case demonstrates the unusual but severe damage that can occur with the abuse of fluorinated hydrocarbons.

Analysing destruction channels of interstellar hydrocarbon anions with a 22pol ion-trap

Energy Technology Data Exchange (ETDEWEB)

Endres, Eric; Lakhmanskaya, Olga; Best, Thorsten; Hauser, Daniel; Kumar, Sunil; Wester, Roland [Universitaet Innsbruck, Institut fuer Ionenphysik und Angewandte Physik (Austria)

2014-07-01

In the interstellar medium (ISM), ion-molecule reactions are considered to play a key role in the formation of complex molecules. The detection of the first interstellar anions, which happen to be carbon chain anions, has raised new interest in the quantitative composition of the ISM and the underlying reaction network. To understand the observed abundance of these carbon chain anions, a detailed analysis of the possible destruction channels is indispensable. A cryogenic 22-pol radio frequency ion trap is an ideal tool to observe reactions that take place slowly, such as carbon chain anions with molecular hydrogen. Furthermore, measurements over a large temperature scale are feasible. Longitudinal optical access to the trap also provides the possibility to make precise photodetachment measurements. Temperature dependent measurements of the reaction rates for the reaction between hydrocarbon chain anions and H{sub 2} are presented.

Reactions of model compounds in the presence of pyrene and MoS sub 2 to simulate coprocessing

Energy Technology Data Exchange (ETDEWEB)

Ting, P.-S.; Curtis, C.W.; Cronauer, D.C. (Auburn University, Auburn, AL (USA). Chemical Engineering Dept.)

Catalytic reactions of pyrene using in situ generated MoS{sub 2} from molybdenum naphthenate and excess sulfur were evaluated in the presence of added model species, both hydrocarbons and heteroatomic species. The added hydrocarbons and heteroatomic compounds containing oxygen and sulfur had little effect on the hydrogenation of pyrene at either 400 or 425{degree}C, but quinoline at 400{degree}C reduced the hydrogenation of pyrene by half. Reactions at 425{degree}C also reduced the hydrogenation of pyrene by half regardless of the added model species. The added model species underwent different degrees of reaction: the hydrocarbons underwent little or no reaction, dibenzofuran showed little hydrodeoxygenation, dibenzothiophene yielded substantial hydrodesulfurization and quinoline was almost totally hydrodenitrogenated. The addition of quinoline at increasing concentration resulted in substantial lowering of pyrene hydrogenation and quinoline hydrodenitrogenation. Introduction of quinoline at a low concentration of 0.4 wt% gave a pyrene hydrogenation rate constant of 0.073 min{sup -1} at 400{degree}C while an increase in quinoline to 10.0 wt% yielded a rate constant of 0.020 min{sup -1}. 21 refs., 7 figs., 6 tabs.

A STUDY ON ADVERSE DRUG REACTIONS INVOLVING CENTRAL NERVOUS SYSTEM, ITS SEVERITY AND CAUSALITY ASSESSMENT IN PEDIATRIC PATIENTS ADMITTED TO A TERTIARY CARE HOSPITAL

Directory of Open Access Journals (Sweden)

Arati

2015-09-01

Full Text Available A retrospective study was conducted in Department of pediatrics SCB Medical College and SVPPGIP for a period of 2 years i.e. September 2012 to August 2014 . All the patients from birth to 14 years admitted to the pediatric ward in this study were under ADR surveillance. Patients admitted to our hospital with adverse drug reaction o r patients developing adverse drug reaction in our hospital were studied; only those cases where the central nervous system was involved were taken in our study. The cases were compiled and the causality of offending drugs was found using WHO - UMC causality assessment score. The severity of drug reaction in every case was determined by using HARTWIG’s severity scoring scale. Total 350 Adverse reactions were reported in this period with prevalence rate of 2.04% i.e. 20 out of 1000 children faced ADR due to dr ugs, with annual incidence rate of 0.9% and 1.14% over two years. Out of total 350 cases dermatological system was most commonly involved i.e. 207 cases (59.14%. This is followed by involvement of central nervous system 46 number of cases (13.14%. The GI system was involved in 34 cases i.e. (9.71%. Life threatening reactions like anaphylaxis, angioedema and shock like immediate life threatening ADRs were reported in 16 cases. Our study group was the patient in whom the ADR involved the CNS. Out of 46 suc h cases, there were 25 female and 21 male. Various reaction due to drug were encephalopathy , eps, febrile seizure, tremor, head reeling, ototoxicity, persistant cry, pseudotumor cerebri, psychosis, seizure, status epilepticus, toxic amblyopia, tremor, atax ia etc. The most common CNS manifestation was Extra pyramidal side effects (EPS involving 21% of cases. The most common Drug causing CNS manifestation was ATT (HRZE causing blindness, Eps, psychosis , toxic amblyopia blindness etc.

Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

Science.gov (United States)

Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

2014-04-15

Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs. Copyright © 2013 Elsevier B.V. All rights reserved.

Flat Graphene-Enhanced Electron Transfer Involved in Redox Reactions.

Science.gov (United States)

Pan, Meilan; Zhang, Yanyang; Shan, Chao; Zhang, Xiaolin; Gao, Guandao; Pan, Bingcai

2017-08-01

Graphene is easily warped in the out-of-plane direction because of its high in-plane Young's modulus, and exploring the influence of wrinkled graphene on its properties is essential for the design of graphene-based materials for environmental applications. Herein, we prepared wrinkled graphene (WGN-1 and WGN-2) by thermal treatment and compared their electrochemical properties with those of flat graphene nanosheets (FGN). FGN exhibit activities that are much better than those of wrinkled graphene nanosheets (WGN), not only in the electrochemical oxidation of methylene blue (MB) but also in the electrochemical reduction of nitrobenzene (NB). Transformation ratios of MB and NB in FGN, WGN-1, and WGN-2 were 97.5, 80.1, and 57.9% and 94.6, 92.1, and 81.2%, respectively. Electrochemical impedance spectroscopy and the surface resistance of the graphene samples increased in the following order: FGN reaction charges transfer faster across the reaction interfaces and along the surface of FGN than that of WGN, and wrinkles restrict reaction charge transfer and reduce the reaction rates. This study reveals that the morphology of the graphene (flat or wrinkle) greatly affects redox reaction activities and may have important implications for the design of novel graphene-based nanostructures and for our understanding of graphene wrinkle-dependent redox reactions in environmental processes.

Light hydrocarbons as redox and temperature indicators in the geothermal field of El Tatio (northern Chile)

Energy Technology Data Exchange (ETDEWEB)

Tassi, F. [University of Florence (Italy). Dept. of Earth Sciences; Martinez, C. [University Catolica del Norte, Antofagasta (Chile). Dept. of Earth Science; Vaselli, O. [University of Florence (Italy). Dept. of Earth Sciences; Institute of Geosciences and Earth Resources, Florence (Italy). National Council of Research; Capaccioni, B. [University of Urbino (Italy). Institute of Volcanology and Geochemistry; Viramonte, J. [National University of Salta (Argentina). Institute GEONORTE and CONICET

2005-11-15

El Tatio (northern Chile), one of the largest geothermal fields of South America, is presently undergoing a new program of geothermal exploration, after the failure of the first exploration phase in the early 1970s. The geochemical features of the fluid discharges characterizing this system mainly consist of boiling pools and fumaroles, and represent the result of a complex mixing process involving 3 main components: (i) hydrothermal; (ii) atmospheric; (iii) magmatic. Chemical reactions involving light hydrocarbons equilibrate at higher temperature than those directly measured in the geothermal wells and calculated on the basis of the composition of the inorganic gas species. This suggests that in the deeper parts of the hydrothermal system temperatures higher than 300{sup o}C may be achieved. Such results can have a strong impact for the evaluation of the potential resources of this geothermal system. Moreover, the chemical characteristics of the organic gas fraction allow the assessment of the chemical-physical conditions governing the geochemical processes acting on geothermal fluids at depth. (author)

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.)

Molecular networks in Position, Momentum, and Phase Space: A Case Study on Simple Hydrocarbons

DEFF Research Database (Denmark)

Schmider, Hartmut; Ho, Minhhuy

1996-01-01

are identified in a series of nine small hydrocarbonic molecules, and the resulting "molecular graphs" are interpreted in terms of symmetry and topology. For the example of a symmetric SN2 reaction, it is shown that the topology of the Husimi function based graphs can be useful for the classification of chemical...

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

Energy Technology Data Exchange (ETDEWEB)

Nehr, Sascha

2012-07-01

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

Detection of hydrocarbons in irradiated foods

International Nuclear Information System (INIS)

Miyahara, Makoto; Maitani, Tamio; Saito, Akiko; Kamimura, Tomomi; Nagasawa, Taeko; Kobayashi, Yasuo; Ito, Hitoshi

2003-01-01

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)

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)

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

Tolerance of Antarctic soil fungi to hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Hughes, Kevin A.; Bridge, Paul; Clark, Melody S. [British Antarctic Survey, Natural Environment Research Council, High Cross, Madingley Road, Cambridge CB3 0ET (United Kingdom)

2007-01-01

Little is known about the effects of hydrocarbons and fuel oil on Antarctic filamentous fungi in the terrestrial Antarctic environment. Growth of fungi and bacteria from soils around Rothera Research Station (Adelaide Island, Antarctic Peninsula) was assessed in the presence of ten separate aromatic and aliphatic hydrocarbons [marine gas oil (MGO), dodecane, hexadecane, benzoic acid, p-hydroxybenzoic acid, toluene, phenol, biphenyl, naphthalene and m- and p-xylenes with ethylbenzene]. Aromatic hydrocarbons inhibited soil microbial growth more than aliphatic hydrocarbons. Soil microorganisms from a moss patch, where little previous impact or hydrocarbon contamination had occurred, were less tolerant of hydrocarbons than those from high impact sites. Fungal growth rates of Mollisia sp., Penicillium commune, Mortierella sp., Trichoderma koningii, Trichoderma sp. and Phoma herbarum were assessed in the presence of hydrocarbons. Generally, aromatic hydrocarbons inhibited or stopped hyphal extension, though growth rates increased with some aliphatic hydrocarbons. Hyphal dry weight measurements suggested that Mortierella sp. may be able to use dodecane as sole carbon and energy source. Hydrocarbon-degrading Antarctic fungi may have use in future hydrocarbon spill bioremediation. (author)

Hydrocarbon delineation in Muskeg : distinguishing biogenic from petrogenic sources

Energy Technology Data Exchange (ETDEWEB)

Harris, C. [UMA Engineering Ltd., Victoria, BC (Canada)

2006-07-01

The quantification of biogenic versus petrogenic hydrocarbons from an emulsion pipeline in a Muskeg setting in northeastern British Columbia was examined. This presentation provided an introduction and discussion of the challenges in Muskeg environments. It introduced the objectives of the study and the analytical approach. Some supporting literature involving studies on the distribution and origin of hydrocarbons in estuary sediments was also cited. Box plots of the physical and chemical characteristics of soil and chromatograms of gas chromatography flame ionization detector (GC-FID) and gas chromatography mass spectrometry (GC-MS) were presented. Last, the approach to establish a true biogenic source and the recommended analytical program and corrections for biogenic input were discussed. The definition of contaminated peat was introduced. tabs., figs.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

Science.gov (United States)

Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

1984-01-01

The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

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).

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

Science.gov (United States)

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Branched alkanes from ancient and modern sediments: isomer discrimination by GC/MS with multiple reaction monitoring

Energy Technology Data Exchange (ETDEWEB)

Summons, R.E.

1987-01-01

Linked scanning of a tandem sector mass spectrometer has been used to identify abundant, first field free region (FFR1) unimolecular fragmentations in branched and isoprenoid hydrocarbons. The most intense, structure-specific reactions were selected to establish multiple reaction monitoring (MRM) parameters for GC/MS analysis. This methodology has been used to study the identify of co-eluting and closely eluting hydrocarbon biomarkers from modern and ancient sediments and from extant microorganisms. Some sediments of Cambrian and Proterozoic age have been found to contain suites of monomethylalkanes with all possible isomers present and with little apparent preference for the site of branching.

Endophytic Bacteria Associated with Hieracium piloselloides: Their Potential for Hydrocarbon-Utilizing and Plant Growth-Promotion.

Science.gov (United States)

Pawlik, Małgorzata; Piotrowska-Seget, Zofia

2015-01-01

The aim of this study was to assess the potential of 18 crude-oil-degrading endophytic bacteria for removal of hydrocarbons and promotion of plant growth. Strains were isolated from Hieracium piloselloides (tall hawkweed), which grows in soil heavily polluted with petroleum hydrocarbons. Bacteria from the genus Pseudomonas were abundant among the isolates. The potential for hydrocarbon degradation was evaluated by polymerase chain reaction (PCR) analyses of the genes alkB, alkH, C23O, P450, and pah. It was found that 88.89% of the endophytic bacteria contained gene-encoding polycyclic aromatic hydrocarbon (PAH) initial dioxygenase, 61% possessed the 2,3-catechol dioxygenase gene, and 39% of strains that were tested had the cytochrome P-450 hydroxylase gene. All isolates were capable of producing indole-3-acetic acid (1.8-76.4 μg/ml). Only 17% of them were able to produce siderophores, excrete cellulase, and solubilize phosphate. Hydrogen cyanide synthesis occurred in 33% of endophytic bacteria. The 1-aminocyclopropane-1-carboxylate deaminase activity in isolates that were screened was in the range of 2.6 to 74.1 μmol α-ketobutyrate/mg/h. This feature of the bacteria indicated that isolates may enhance the phytoremediation process. Data suggest that crude-oil-degrading endophytic bacteria possess potential to be promising candidates for enhancement of phytoremediation of hydrocarbon-contaminated soil. Further evaluation of these bacteria is needed in order to assess the role played in the degradation of petroleum hydrocarbons.

A Field Scale Investigation of Enhanced Petroleum Hydrocarbon Biodegradation in the Vadose Zone Combining Soil Venting as an Oxygen Source with Moisture and Nutrient Addition

Science.gov (United States)

1990-01-01

herbicides, insecticides, and fungicides is dependent upon both biotic and abiotic reactions, and the rate of these reactions determines the required...The most commonly isolated I hydrocarbon degrading fungi in decreasing order include: Trichoderma , i Penicillium, Aspergillus, and Mortierella (Dragun

Dynamics of O(3P) Reactions with Gaseous Liquid and Solid Hydrocarbons

National Research Council Canada - National Science Library

Hase, William L

2006-01-01

...) were applied to model reactions, including 0 + ethane and related reactions. In the second phase, a semiempirical quantum chemistry method, PM3-SRP, was developed by modifying and reparametrizing the standard PM3 method to fit the ab initio data...

Offshore hydrocarbon releases statistics, 1996. For the period 1.10.92 to 31.3.96 inclusive

International Nuclear Information System (INIS)

1996-10-01

Data on offshore hydrocarbon release incidents, which occurred between 1 October 1992 and 31 March 1996 and which were voluntarily reported to the United Kingdom Health and Safety Executive are included in this report. It aims to provide data from the Hydrocarbon Releases Database for the offshore industry to use in its Offshore Safety Cases, and especially in cases where quantified risk assessment (QRA) is involved. (UK)

DFT studies of hydrocarbon combustion on metal surfaces.

Science.gov (United States)

Arya, Mina; Mirzaei, Ali Akbar; Davarpanah, Abdol Mahmood; Barakati, Seyed Masoud; Atashi, Hossein; Mohsenzadeh, Abas; Bolton, Kim

2018-02-02

Catalytic combustion of hydrocarbons is an important technology to produce energy. Compared to conventional flame combustion, the catalyst enables this process to operate at lower temperatures; hence, reducing the energy required for efficient combustion. The reaction and activation energies of direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces were investigated using density functional theory (DFT). The data obtained for the Ag, Au, Al, Cu, Rh, Pt, and Pd surfaces were used to investigate the validity of the Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) relations for this reaction on these surfaces. These relations were found to be valid (R 2  = 0.94 for the BEP correlation and R 2  = 1.0 for the TSS correlation) and were therefore used to estimate the energetics of the combustion reaction on Ni, Co, and Fe surfaces. It was found that the estimated transition state and activation energies (E TS  = -69.70 eV and E a  = 1.20 eV for Ni, E TS  = -87.93 eV and E a  = 1.08 eV for Co and E TS  = -92.45 eV and E a  = 0.83 eV for Fe) are in agreement with those obtained by DFT calculations (E TS  = -69.98 eV and E a  = 1.23 eV for Ni, E TS  = -87.88 eV and E a  = 1.08 eV for Co and E TS  = -92.57 eV and E a  = 0.79 eV for Fe). Therefore, these relations can be used to predict energetics of this reaction on these surfaces without doing the time consuming transition state calculations. Also, the calculations show that the activation barrier for CH dissociation decreases in the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe.

Hot atom reactions involving multivalent and univalent species. Progress report, February 1979-January 1980

International Nuclear Information System (INIS)

Tang, Y.N.

1980-01-01

The major progress during this period was in the study of recoil 31 Si and recoil 11 C reactions and in the initiation of the studies on the interaction of molecular tritium on solid surfaces. For the recoil 31 Si systems, heterogeneous hydrogenation experiments have been designed to positively confirm that a major unknown product, derived from the interaction of 31 Si atoms with 1,3-butadiene, is 1-silacyclopenta-2,4-diene. This compound has been shown to be very sensitive to γ-ray irradiation and to be thermally unstable at a temperature higher than 100 0 C. Another recoil 31 Si experiment was designed to review the mechanism of the 31 Si abstraction reactions. From the fact that high yields of [ 31 Si]-1-fluorosilacyclopent-3-ene were obtained as a product from a mixture of PH 3 and PF 3 together with 1,3-butadiene, the stepwise abstraction mechanism is definitely much more predominant than the possible simultaneous abstraction. Other recoil 31 Si works involved a detailed systematic composition study of 31 SiF 2 reactions with 1,3-butadiene, some neon moderator studies, and the continuation of the studies on the reactions of 31 SiF 2 and 31 SiH 2 with conjugated hexadienes. By using 2- 14 C-propanone and 1,3- 14 C-propanone, the mechanism of solvent-free oxidative cleavage of propanone by KMnO 4 was elucidated. Information thus derived was used to degradate the 11 C-labelled propadiene derived from the reactions of recoil 11 C atoms with ethylene. Results indicate that 73% of the 11 C-labelled propadiene was center-labelled. This value was observed to change with additives. Various mechanistic studies on the heterogeneous interactions of molecular T 2 on solid surfaces such as Pd supported on active carbon have been initiated

Isolation of microorganisms with capability to degrade polycyclic aromatic hydrocarbons (PATH )

International Nuclear Information System (INIS)

Vargas, M.C; Ramirez, N.E; Rueda, S.M; Sanchez, F.N

1996-01-01

This paper summarizes a work conducted on the isolation of microorganisms of contaminated sediments with a high percentage of hydrocarbons aromatic polynuclear (Polynuclear Aromatic Hydrocarbons, PAHS) The methodology involved two selection systems called fast route and slow route in which exposure periods and contaminant concentrations are the key determinants. The microorganisms isolated through the slow route system are more likely to be successful in degrading high molecular weight PAH'S. The six strains obtained through the fast route system were able to grow on low molecular weight PAH's showing preference towards the first four compounds of the sixteen demanded by the EPA (Environmental Protection Agency)

Versatility of hydrocarbon production in cyanobacteria.

Science.gov (United States)

Xie, Min; Wang, Weihua; Zhang, Weiwen; Chen, Lei; Lu, Xuefeng

2017-02-01

Cyanobacteria are photosynthetic microorganisms using solar energy, H 2 O, and CO 2 as the primary inputs. Compared to plants and eukaryotic microalgae, cyanobacteria are easier to be genetically engineered and possess higher growth rate. Extensive genomic information and well-established genetic platform make cyanobacteria good candidates to build efficient biosynthetic pathways for biofuels and chemicals by genetic engineering. Hydrocarbons are a family of compounds consisting entirely of hydrogen and carbon. Structural diversity of the hydrocarbon family is enabled by variation in chain length, degree of saturation, and rearrangements of the carbon skeleton. The diversified hydrocarbons can be used as valuable chemicals in the field of food, fuels, pharmaceuticals, nutrition, and cosmetics. Hydrocarbon biosynthesis is ubiquitous in bacteria, yeasts, fungi, plants, and insects. A wide variety of pathways for the hydrocarbon biosynthesis have been identified in recent years. Cyanobacteria may be superior chassis for hydrocabon production in a photosynthetic manner. A diversity of hydrocarbons including ethylene, alkanes, alkenes, and terpenes can be produced by cyanobacteria. Metabolic engineering and synthetic biology strategies can be employed to improve hydrocarbon production in cyanobacteria. This review mainly summarizes versatility and perspectives of hydrocarbon production in cyanobacteria.

Subduction zone earthquake probably triggered submarine hydrocarbon seepage offshore Pakistan

Science.gov (United States)

Fischer, David; José M., Mogollón; Michael, Strasser; Thomas, Pape; Gerhard, Bohrmann; Noemi, Fekete; Volkhard, Spiess; Sabine, Kasten

2014-05-01

Seepage of methane-dominated hydrocarbons is heterogeneous in space and time, and trigger mechanisms of episodic seep events are not well constrained. It is generally found that free hydrocarbon gas entering the local gas hydrate stability field in marine sediments is sequestered in gas hydrates. In this manner, gas hydrates can act as a buffer for carbon transport from the sediment into the ocean. However, the efficiency of gas hydrate-bearing sediments for retaining hydrocarbons may be corrupted: Hypothesized mechanisms include critical gas/fluid pressures beneath gas hydrate-bearing sediments, implying that these are susceptible to mechanical failure and subsequent gas release. Although gas hydrates often occur in seismically active regions, e.g., subduction zones, the role of earthquakes as potential triggers of hydrocarbon transport through gas hydrate-bearing sediments has hardly been explored. Based on a recent publication (Fischer et al., 2013), we present geochemical and transport/reaction-modelling data suggesting a substantial increase in upward gas flux and hydrocarbon emission into the water column following a major earthquake that occurred near the study sites in 1945. Calculating the formation time of authigenic barite enrichments identified in two sediment cores obtained from an anticlinal structure called "Nascent Ridge", we find they formed 38-91 years before sampling, which corresponds well to the time elapsed since the earthquake (62 years). Furthermore, applying a numerical model, we show that the local sulfate/methane transition zone shifted upward by several meters due to the increased methane flux and simulated sulfate profiles very closely match measured ones in a comparable time frame of 50-70 years. We thus propose a causal relation between the earthquake and the amplified gas flux and present reflection seismic data supporting our hypothesis that co-seismic ground shaking induced mechanical fracturing of gas hydrate-bearing sediments

Heterobimetallic Zeolite, InV-ZSM-5, Enables Efficient Conversion of Biomass Derived Ethanol to Renewable Hydrocarbons.

Science.gov (United States)

Narula, Chaitanya K; Li, Zhenglong; Casbeer, Erik M; Geiger, Robert A; Moses-Debusk, Melanie; Keller, Martin; Buchanan, Michelle V; Davison, Brian H

2015-11-03

Direct catalytic conversion of ethanol to hydrocarbon blend-stock can increase biofuels use in current vehicles beyond the ethanol blend-wall of 10-15%. Literature reports describe quantitative conversion of ethanol over zeolite catalysts but high C2 hydrocarbon formation renders this approach unsuitable for commercialization. Furthermore, the prior mechanistic studies suggested that ethanol conversion involves endothermic dehydration step. Here, we report the complete conversion of ethanol to hydrocarbons over InV-ZSM-5 without added hydrogen and which produces lower C2 (dehydration step is not necessary. Thus, our method of direct conversion of ethanol offers a pathway to produce suitable hydrocarbon blend-stock that may be blended at a refinery to produce fuels such as gasoline, diesel, JP-8, and jet fuel, or produce commodity chemicals such as BTX.

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

Science.gov (United States)

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

2006-12-01

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

Reflections about the modelling of unconfined explosions of air-hydrocarbon mixtures

International Nuclear Information System (INIS)

Hendrickx, S.; Lannoy, A.

1983-01-01

To design nuclear power plants structures, an evaluation of hazards which can be induced by the industrial activities is needed. These hazards namely involve explosions of flamable air-hydrocarbon gas clouds. Such clouds can drift before ignition, and, when ignited, the generated pressure wave can cause serious damage, even far from the initial accident location. When the designs an industrial plant, the designer has to predict the overpressures capable of jeopardizing the safety functions of the plant. The analysis of real accidental explosions which have actually occurred, on the basis of a total explosion yield and the TNT equivalency concept, is a first step. Indeed, it allows a total explosion yield to be calculated, an empirical TNT equivalent of hydrocarbon to be deducted. Unfortunately, this TNT equivalency concept is scientifically not satisfying. The modelling of an unconfined air-hydrocarbon detonation can be used for safety analysis, if we assume that an unconfined explosion can be a detonation, which is unlikely. (orig./WL)

Rates for some reactions involving 42Ca and 44Ca

International Nuclear Information System (INIS)

Cheng, C.W.; King, J.D.

1980-01-01

Ground-state reaction rates have been deduced from recent cross section measurements for the 42 CA(α, n) 45 Ti, 42 Ca(p, γ) 43 Sc, and 44 Ca(p, n) 44 Sc reactions. Comparison of these rates with those calculated from a statistical model of nuclear reactions. (Woosley et al) shows good agreement for the first two, but the 44 Ca(p, n) rate is more than a factor of 2 less than the theoretical prediction. Stellar reaction rates have been derived from the ground-state rates by multiplying the ground-state rates by the ratio of stellar to ground-state rates given by the statistical model. Both ground-state and stellar rates have been represented by analytic functions of the temperature. The role of these reactions in the approach to quasi-equilibrium during explosive silicon burning is discussed

Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

International Nuclear Information System (INIS)

Xuelei Chu; Ohmoto, Hiroshi

1991-01-01

For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

Monitoring biodegradation of hydrocarbons by stable isotope fractionation

Science.gov (United States)

Dorer, Conrad; Fischer, Anko; Herrmann, Steffi; Richnow, Hans-Hermann; Vogt, Carsten

2010-05-01

In the last decade, several studies have demonstrated that stable isotope tools are highly applicable for monitoring anaerobic biodegradation processes. An important methodological approach is to characterize distinct degradation pathways with respect to the specific mechanism of C-H-bond cleavage and to quantify the extent of biodegradation by compound specific isotope analysis (CSIA). Here, enrichment factors (ɛbulk) needed for a CSIA field site approach must be determined in laboratory reference experiments. Recent research results from different laboratories have shown that single ɛbulk values for similar degradation pathways can be highly variable; thus, the use of two-dimensional compound specific isotope analysis (2D-CSIA) has been encouraged for characterizing biodegradation pathways more precisely. 2D-CSIA for hydrocarbons can be expressed by the slope of the linear regression for hydrogen versus carbon discrimination known as lambda ≈ ɛHbulk/ɛCbulk. We determined the carbon and hydrogen isotope fractionation for the biodegradation of benzene, toluene and xylenes by various reference cultures. Specific enzymatic reactions initiating different biodegradation pathways could be distinguished by 2D-CSIA. For the aerobic di- and monohydroxylation of the benzene ring, lambda values always lower than 9 were observed. Enrichment cultures degrading benzene anaerobically produced significant different values: lambda values between 8-19 were oberved for nitrate-reducing consortia, whereas sulfate-reducing and methanogenic consortia showed always lambda values greater than 20 [1,2]. The observed variations suggest that (i) aerobic benzene biodegradation can be distinguished from anaerobic biodegradation, and (ii) that more than a single mechanism seems to exist for the activation of benzene under anoxic conditions. lambda values for anaerobic toluene degradation initiated by the enzyme benzylsuccinate synthase (BSS) ranged from 4 to 41, tested with strains using

Predicting hydrocarbon release from soil

International Nuclear Information System (INIS)

Poppendieck, D.; Loehr, R.C.

2002-01-01

'Full text:' The remediation of hazardous chemicals from soils can be a lengthy and costly process. As a result, recent regulatory initiatives have focused on risk-based corrective action (RBCA) approaches. Such approaches attempt to identify the amount of chemical that can be left at a site with contaminated soil and still be protective of human health and the environment. For hydrocarbons in soils to pose risk to human heath and the environment, the hydrocarbons must be released from the soil and accessible to microorganisms, earthworms, or other higher level organisms. The sorption of hydrocarbons to soil can reduce the availability of the hydrocarbon to receptors. Typically in soils and sediments, there is an initial fast release of a hydrocarbon from the soil to the aqueous phase followed by a slower release of the remaining hydrocarbon to the aqueous phase. The rate and extent of slow release can influence aqueous hydrocarbon concentrations and the fate and transport of hydrocarbons in the subsurface. Once the fast fraction of the chemical has been removed from the soil, the remaining fraction of a chemical may desorb at a rate that natural mechanisms can attenuate the released hydrocarbon. Hence, active remediation may be needed only until the fast fraction has been removed. However, the fast fraction is a soil and chemical specific parameter. This presentation will present a tier I type protocol that has been developed to quickly estimate the fraction of hydrocarbons that are readily released from the soil matrix to the aqueous phase. Previous research in our laboratory and elsewhere has used long-term desorption (four months) studies to determine the readily released fraction. This research shows that a single short-term (less than two weeks) batch extraction procedure provides a good estimate of the fast released fraction derived from long-term experiments. This procedure can be used as a tool to rapidly evaluate the release and bioavailability of

Hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1927-02-22

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

Prospects for development of hydrocarbon raw materials resources reproduction

Science.gov (United States)

Vertakova, Y. V.; Babich, T. N.; Polozhentseva, Y. S.; Zvyagintsev, G. L.

2017-10-01

The article presents data on the influence of factors in the field of innovative technology of thermocatalytic depolymerization of solid household wastes (SHW) on the efficiency and prospects for the development of technogenic hydrocarbon raw materials resource reproduction. Process thermodynamics, reactions kinetics, the mechanism of thermolysis of secondary polymers in organic solvents have been studied by means of laboratory experiments. It is shown that different morphological groups of wastes dissolve practically at the same rate at temperatures of 250-310°C. A homogeneous product is formed in the liquid phase; the spread of values for the elements lies in the interval of 1.5-4.5 %; technological requirements of the stages of formation of boiler fuels are satisfied. Using the principles of patent analysis, new techniques of processing household waste components are proposed. The basics of energy-efficient and energy-saving processes of technogenic hydrocarbon raw materials resource reproduction have been laid. The possibility of increasing the production payback and intensification is shown. Ecological and demographic safety for population and technical and economic benefits from SHW processing are achieved.

Syngas Conversion to Gasoline-Range Hydrocarbons over Pd/ZnO/Al2O3 and ZSM-5 Composite Catalyst System

Energy Technology Data Exchange (ETDEWEB)

Dagle, Robert A.; Lizarazo Adarme, Jair A.; Lebarbier, Vanessa MC; Gray, Michel J.; White, James F.; King, David L.; Palo, Daniel R.

2014-07-01

A composite Pd/ZnO/Al2O3-HZSM-5 (Si/Al=40) catalytic system was evaluated for the synthesis of gasoline-range hydrocarbons directly from synthesis gas. Bifunctional catalyst comprising PdZn metal and acid sites present the required catalytically active sites necessary for the methanol synthesis, methanol dehydration, and methanol-to-gasoline reactions. This system provides a unique catalytic pathway for the production of liquid hydrocarbons directly from syngas. However, selectivity control is difficult and poses many challenges. The composite catalytic system was evaluated under various process conditions. Investigated were the effects of temperature (310-375oC), pressure (300-1000 psig), time-on-stream (50 hrs), and gas-hour space velocity (740-2970 hr-1), using a H2/CO molar syngas ratio of 2.0. By operating at the lower end of the temperature range investigated, liquid hydrocarbon formation was favored, as was decreased amounts of undesirable light hydrocarbons. However, lower operating temperatures also facilitated undesirable CO2 formation via the water-gas shift reaction. Higher operating pressures slightly favored liquid synthesis. Operating at relatively low pressures (e.g. 300 psig) was made possible, whereas for methanol synthesis alone higher pressure are usually required to achieve similar conversion levels (e.g. 1000 psig). Thermodynamic constraints on methanol synthesis are eased by pushing the equilibrium through hydrocarbon formation. Catalytic performance was also evaluated by altering Pd and Zn composition of the Pd/ZnO/Al2O3 catalyst. Of the catalysts and conditions tested, selectivity toward liquid hydrocarbon was highest when using a 5% Pd metal loading and Pd/Zn molar ratio of 0.25 and mixed with HZMS-5, operating at 310oC and 300 psig, CO conversion was 43 % and selectivity (carbon weight basis) to hydrocarbons was 49 wt. %. Of the hydrocarbon fraction, 44wt. % was in the C5-C12 liquid product range and consisted primarily of aromatic

The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

Science.gov (United States)

Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

2017-09-07

A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

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.

A new HYSYS model for underground gasification of hydrocarbons under hydrothermal conditions

KAUST Repository

Alshammari, Y.M.

2014-08-01

A new subsurface process model was developed using the ASPEN HYSYS simulation environment to analyse the process energy and gasification efficiency at steady-state equilibrium conditions. Injection and production wells were simulated using the HYSYS pipe flow utilities which makes use of the Beggs and Brill flow correlation applicable for vertical pipes. The downhole reservoir hydrothermal reactions were assumed to be in equilibrium, and hence, the Gibbs reactor was used. It was found that high W/C ratios and low O/C ratios are required to maximise gasification efficiency at a constant hydrocarbon feed flowrate, while the opposite is true for the energy efficiency. This occurs due to the dependence of process energy efficiency on the gas pressure and temperature at surface, while the gasification efficiency depends on the gas composition which is determined by the reservoir reaction conditions which affects production distribution. Another effect of paramount importance is the increase in reservoir production rate which was found to directly enhance both energy and gasification efficiency showing conditions where the both efficiencies are theoretically maximised. Results open new routes for techno-economic assessment of commercial implementation of underground gasification of hydrocarbons. © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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

Directory of Open Access Journals (Sweden)

Maria Cristina Collivignarelli

2018-06-01

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

Economic analysis of hydrocarbon exploration by simulation with geological uncertainties (exploratory wells)

International Nuclear Information System (INIS)

Chungcharoen, E.

1997-01-01

A model was developed to help determine the future development of hydrocarbon reserves. The uncertainties of geological parameters were incorporated into the model in an effort to provide an assessment of the distribution of total hydrocarbon discoveries that are expected to be recovered as a result of exploration activity. The economic parameters were also incorporated into the model in an effort to determine the economic worth of multiple-wells exploration activity. The first part of this study included the geological parameters in the initial field size distribution and the number of fields distribution. Dry hole data was also considered to reflect the exploration risk. The distribution of total hydrocarbon discoveries for a selected number of exploratory wells was determined. The second part of the study included the economic parameters such as the price of oil and gas and the cost of exploration, development and production. The distribution of the number of discoveries and the distribution of total hydrocarbon discoveries was compared to produce a probability distribution of the net present value of a proposed exploration program. The offshore Nova Scotia Shelf basin was chosen for testing the methodology. Several scenarios involving changes in economic parameters were shown. This methodology could help in determining future development programs for hydrocarbon reserves. The methodology can also help governments in policy making decisions regarding taxes and royalty regimes for exploration programs

Steam cracking of hydrocarbons 6. Effect of dibenzyl sulfide and dibenzyl disulfide on reaction kinetics and coking

NARCIS (Netherlands)

Bajus, M.; Baxa, J.; Leclercq, P.A.; Rijks, J.A.

1983-01-01

The influence of aromatic sulfides on the kinetics and selectivity of hydrocarbon conversion by steam cracking and on pyrolytic coke formation was investigated in stainless steel tubular reactors with relatively large inner surface.The rate of decomposition of heptane (at 700 ‘C, 100 kPa, and a mass

LOW TEMPERATURE FORMATION OF NITROGEN-SUBSTITUTED POLYCYCLIC AROMATIC HYDROCARBONS (PANHs)—BARRIERLESS ROUTES TO DIHYDRO(iso)QUINOLINES

Energy Technology Data Exchange (ETDEWEB)

Parker, Dorian S. N.; Yang, Tao; Dangi, Beni B.; Kaiser, Ralf I. [Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States); Bera, Partha P.; Lee, Timothy J., E-mail: ralfk@hawaii.edu, E-mail: Timothy.J.Lee@nasa.gov [Space Science and Astrobiology Division, NASA Ames Research Center, Moffett Field, Mountain View, CA 94035 (United States)

2015-12-20

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.

Thermodynamic functions of hydration of hydrocarbons at 298.15 K and 0.1 MPa

Science.gov (United States)

Plyasunov, Andrey V.; Shock, Everett L.

2000-02-01

An extensive compilation of experimental data yielding the infinite dilution partial molar Gibbs energy of hydration Δ hGO, enthalpy of hydration Δ hHO, heat capacity of hydration Δ hCpO, and volume V2O, at the reference temperature and pressure, 298.15 K and 0.1 MPa, is presented for hydrocarbons (excluding polyaromatic compounds) and monohydric alcohols. These results are used in a least-squares procedure to determine the numerical values of the corresponding properties of the selected functional groups. The simple first order group contribution method, which in general ignores nearest-neighbors and steric hindrance effects, was chosen to represent the compiled data. Following the precedent established by Cabani et al. (1981), the following groups are considered: CH 3, CH 2, CH, C for saturated hydrocarbons; c-CH 2, c-CH, c-C for cyclic saturated hydrocarbons; CH ar, C ar for aromatic hydrocarbons (containing the benzene ring); C=C, C≡C for double and triple bonds in linear hydrocarbons, respectively; c-C=C for the double bond in cyclic hydrocarbons; H for a hydrogen atom attached to the double bond (both in linear and cyclic hydrocarbons) or triple bond; and OH for the hydroxyl functional group. In addition it was found necessary to include the "pseudo"-group I(C-C) to account for the specific interactions of the neighboring hydrocarbon groups attached to the benzene or cyclic ring (in the latter case only for cis-isomers). Results of this study, the numerical values of the group contributions, will allow in most cases reasonably accurate estimations of Δ hGO, Δ hHO, Δ hCpO, and V2O at 298.15 K, 0.1 MPa for many hydrocarbons involved in geochemical and environmental processes.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

International Nuclear Information System (INIS)

Rack, E.P.

1980-02-01

The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, 80 Br, /sup 82m/Br + 82 Br, 82 Br, 82 Br, 128 I, 130 I, and /sup 130m/I + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace elements and trace molecule determinations in biological systems was continued

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

International Nuclear Information System (INIS)

1981-02-01

The stereochemistry of high energy 18 F, /sup 34m/Cl, and 76 Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,γ) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

Energy Technology Data Exchange (ETDEWEB)

1981-02-01

The stereochemistry of high energy /sup 18/F, /sup 34m/Cl, and /sup 76/Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,..gamma..) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied.

Reactivity and selectivity of arenes in reactions with ozone

International Nuclear Information System (INIS)

Vysotskii, Yu.B.; Mestechkin, M.M.; Sivyakova, L.N.; Tyupalo, N.F.

1987-01-01

The reactions of arenes with ozone, distinguished by the variety of products (quinones, aldehydes, acids), are of interest not only from the theoretical standpoint but also are of preparative value in the case of polycyclic hydrocarbons. In this work a quantitative treatment of this reaction is given on the basis of direct kinetic measurements and simple quantum chemical means, permitting its rate constants and the yield of the products to be related to the elements of electronic structure readily subject to quantum mechanical calculation

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

Science.gov (United States)

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

2003-09-01

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

Bioremediation of soils containing petroleum hydrocarbons, chlorinated phenols, and polycyclic aromatic hydrocarbons

International Nuclear Information System (INIS)

Seech, A.; Burwell, S.; Marvan, I.

1994-01-01

Bench-scale treatability investigations, pilot-scale and full-scale bioremediation projects were conducted to evaluate Daramend trademark bioremediation of soils containing petroleum hydrocarbons, heavy oils, paraffins, chlorinated phenols and polycyclic aromatic hydrocarbons (PAHs). Bench-scale investigations were conducted using glass microcosms. Pilot-scale and full-scale demonstrations were conducted at industrial sites and included treatment of excavated soils and sediments in on-site cells constructed using synthetic liners and covered by steel/polyethylene structures as well as in-situ treatment. A total of approximately 5,000 tons of soil was treated. The soil treatment included organic soil amendments, specialized tillage/aeration apparatus, and strict control of soil moisture. The amendments are composed of naturally-occurring organic materials prepared to soil-specific particle size distributions, nutrient profiles, and nutrient-release kinetics. Bench-scale work indicated that in refinery soil containing high concentrations of heavy oils, extractable hydrocarbon concentrations could be rapidly reduced to industrial clean-up criteria, and that the hydrocarbons were fully mineralized with release of CO 2

Characterization of hydrocarbon utilizing fungi from hydrocarbon ...

African Journals Online (AJOL)

Prof. Ogunji

isolated fungi could be useful in the bioremediation of hydrocarbon polluted sites. Keywords: ... Technologies such as mechanical force, burying, evaporation, dispersant application, and ..... The effects of drilling fluids on marine bacteria from a.

Determination of 15 polycyclic aromatic hydrocarbons in aquatic products by solid-phase extraction and GC-MS.

Science.gov (United States)

Liu, Qiying; Guo, Yuanming; Sun, Xiumei; Hao, Qing; Cheng, Xin; Zhang, Lu

2018-02-22

We propose a method for the simultaneous determination of 15 kinds of polycyclic aromatic hydrocarbons in marine samples (muscle) employing gas chromatography with mass spectrometry after saponification with ultrasound-assisted extraction and solid-phase extraction. The experimental conditions were optimized by the response surface method. In addition, the effects of different lyes and extractants on polycyclic aromatic hydrocarbons extraction were discussed, and saturated sodium carbonate was first used as the primary saponification reaction and extracted with 10 mL of ethyl acetate and secondly 1 mol/L of sodium hydroxide and 10 mL of n-hexane were used to achieve better results. The average recovery was 67-112%. Satisfactory data showed that the method has good reproducibility with a relative standard deviation of <13%. The detection limits of polycyclic aromatic hydrocarbons were 0.02-0.13 ng/g. Compared with other methods, this method has the advantages of simple pretreatment, low solvent consumption, maximum polycyclic aromatic hydrocarbons extraction, the fast separation speed, and the high extraction efficiency. It is concluded that this method meets the batch processing requirements of the sample and can also be used to determine polycyclic aromatic hydrocarbons in other high-fat (fish, shrimp, crab, shellfish) biological samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring Trace Hydrocarbons in Silanes

Science.gov (United States)

Lesser, L. A.

1984-01-01

Technique rapid and uses standard analytical equipment. Silane gas containing traces of hydrocarbons injected into carrier gas of moist nitrogen having about 0.2 percent water vapor. Carrier, water and silane pass through short column packed with powdered sodium hydroxide which combines moisture and silane to form nonvolatile sodium silicate. Carrier gas free of silane but containing nonreactive hydrocarbons, pass to silica-gel column where chromatographic separation takes place. Hydrocarbons measured by FID.

A holistic approach to hydrocarbon source allocation in the subtidal sediments of Prince William Sound, Alaska, embayments

International Nuclear Information System (INIS)

Page, D.S.; Bence, A.E.; Burns, W.A.; Boehm, P.D.; Brown, J.S.; Douglas, G.S.

2002-01-01

The complex organic geochemistry record in the subtidal sediments of Prince William Sound, Alaska is a result of much industrial and human activity in the region. Recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska also contribute to the geochemical record. Pyrogenic and petrogenic polycyclic aromatic hydrocarbons (PAH) are introduced regularly to the subtidal sediments at sites of past and present human activities including villages, fish hatcheries, fish camps and recreational campsites as well as abandoned settlements, canneries, sawmills and mines. Hydrocarbon contributions are fingerprinted and quantified using a holistic approach where contributions from multiple sources is determined. The approach involves a good understanding of the history of the area to identify potential sources. It also involves extensive collection of representative samples and an accurate quantitative analysis of the source and sediment samples for PAH analytes and chemical biomarker compounds. Total organic carbon (TOC) does not work in restricted embayments because of a constrained least-square algorithm to determine hydrocarbon sources. It has been shown that sources contributing to the natural petrogenic background are present in Prince William Sound. In particular, pyrogenic hydrocarbons such as combustion products of diesel is significant where there was much human activity. In addition, petroleum produced from the Monterey Formation in California is present in Prince William Sound because in the past, oil and asphalt shipped from California was widely used for fuel. Low level residues of weathered Alaskan North Slope crude oil from the Exxon Valdez spill are also still present. 30 refs., 4 tabs., 2 figs

Hot atom reactions involving multivalent and univalent species. Progress report, February 1979-January 1980

Energy Technology Data Exchange (ETDEWEB)

Tang, Y.N.

1980-01-01

The major progress during this period was in the study of recoil /sup 31/Si and recoil /sup 11/C reactions and in the initiation of the studies on the interaction of molecular tritium on solid surfaces. For the recoil /sup 31/Si systems, heterogeneous hydrogenation experiments have been designed to positively confirm that a major unknown product, derived from the interaction of /sup 31/Si atoms with 1,3-butadiene, is 1-silacyclopenta-2,4-diene. This compound has been shown to be very sensitive to ..gamma..-ray irradiation and to be thermally unstable at a temperature higher than 100/sup 0/C. Another recoil /sup 31/Si experiment was designed to review the mechanism of the /sup 31/Si abstraction reactions. From the fact that high yields of (/sup 31/Si)-1-fluorosilacyclopent-3-ene were obtained as a product from a mixture of PH/sub 3/ and PF/sub 3/ together with 1,3-butadiene, the stepwise abstraction mechanism is definitely much more predominant than the possible simultaneous abstraction. Other recoil /sup 31/Si works involved a detailed systematic composition study of /sup 31/SiF/sub 2/ reactions with 1,3-butadiene, some neon moderator studies, and the continuation of the studies on the reactions of /sup 31/SiF/sub 2/ and /sup 31/SiH/sub 2/ with conjugated hexadienes. By using 2-/sup 14/C-propanone and 1,3-/sup 14/C-propanone, the mechanism of solvent-free oxidative cleavage of propanone by KMnO/sub 4/ was elucidated. Information thus derived was used to degradate the /sup 11/C-labelled propadiene derived from the reactions of recoil /sup 11/C atoms with ethylene. Results indicate that 73% of the /sup 11/C-labelled propadiene was center-labelled. This value was observed to change with additives. Various mechanistic studies on the heterogeneous interactions of molecular T/sub 2/ on solid surfaces such as Pd supported on active carbon have been initiated.

Method of Generating Hydrocarbon Reagents from Diesel, Natural Gas and Other Logistical Fuels

Science.gov (United States)

Herling, Darrell R [Richland, WA; Aardahl, Chris L [Richland, WA; Rozmiarek, Robert T [Middleton, WI; Rappe, Kenneth G [Richland, WA; Wang, Yong [Richland, WA; Holladay, Jamelyn D [Kennewick, WA

2008-10-14

The present invention provides a process for producing reagents for a chemical reaction by introducing a fuel containing hydrocarbons into a flash distillation process wherein the fuel is separated into a first component having a lower average molecular weight and a second component having a higher average molecular weight. The first component is then reformed to produce synthesis gas wherein the synthesis gas is reacted catalytically to produce the desire reagent.

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

International Nuclear Information System (INIS)

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

2009-01-01

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

The use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Douglas, A. [HydroQual, Calgary, AB (Canada)

2008-07-01

HydroQual Laboratories is a wholly-owned subsidiary of Golder Associates and uses biological testing for measuring the effect of toxins and their impact on various links in the food chain in order to evaluate and improve environmental health. It has expertise in various fields of the natural sciences and is ISO certified. This presentation discussed the use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons. The paper presented biotreatability studies run by the company which included bench scale testing on various types of contaminants. The testing involved multiple treatments, determination of dosage, and additional amendments. The strategy may vary based on bench test results and legislation. Trichloroethylene/perchloroethylene remediation strategies were also presented for chemical oxidation; aerobic bioremediation; abiotic remediation; and anaerobic biostimulation and augmentation. Biostimulation was defined as the addition of nutrients to influence the redox potential. The presentation also reviewed anaerobic dehalorespiration; detection methods; DNA isolation; polymerase chain reaction (PCR); and biotreatability case studies. The presentation concluded with some future directions and other uses of PCR. tabs., figs.

Investigation of the combustion kinetics and polycyclic aromatic hydrocarbon emissions from polycaprolactone combustion.

Science.gov (United States)

Chien, Y C; Yang, S H

2013-01-01

Polycaprolactone (PCL) is one of the most attractive biodegradable plastics that has been widely used in medicine and agriculture fields. Because of the large increase in biodegradable plastics usage, the production of waste biodegradable plastics will be increasing dramatically, producing a growing environmental problem. Generally, waste PCL is collected along with municipal solid wastes and then incinerated. This study investigates the combustion kinetics and emission factors of 16 US Environmental Protection Agency (EPA) priority polycyclic aromatic hydrocarbons (PAHs) in the PCL combustion. Experimentally, two reactions are involved in the PCL combustion process, possibly resulting in the emission of carbon dioxide, propanal, protonated caprolactone and very small amounts of PAH produced by incomplete combustion. The intermediate products may continuously be oxidized to form CO2. The emission factors for 16 US EPA priority PAHs are n.d. -2.95 microg/g, which are much lower than those of poly lactic acid and other plastics combustion. The conversion of PCL is 100%. Results from this work suggest that combustion is a good choice for the waste PCL disposal.

Recovering low-boiling hydrocarbons, etc

Energy Technology Data Exchange (ETDEWEB)

Pier, M

1934-10-03

A process is described for the recovery of low-boiling hydrocarbons of the nature of benzine through treatment of liquid carbonaceous materials with hydrogen under pressure at raised temperature, suitably in the presence of catalysts. Middle oils (practically saturated with hydrogen) or higher boiling oils at a temperature above 500/sup 0/ (with or without the addition of hydrogen) containing cyclic hydrocarbons not saturated with hydrogen are changed into low boiling hydrocarbons of the nature of benzine. The cracking takes place under strongly hydrogenating conditions (with the use of a strongly active hydrogenating catalyst or high pressure) at temperatures below 500/sup 0/. If necessary, the constituents boiling below 200/sup 0/ can be reconverted into cyclic hydrocarbons partially saturated with hydrogen. (BLM)

Pyrochlore-type catalysts for the reforming of hydrocarbon fuels

Science.gov (United States)

Berry, David A [Morgantown, WV; Shekhawat, Dushyant [Morgantown, WV; Haynes, Daniel [Morgantown, WV; Smith, Mark [Morgantown, WV; Spivey, James J [Baton Rouge, LA

2012-03-13

A method of catalytically reforming a reactant gas mixture using a pyrochlore catalyst material comprised of one or more pyrochlores having the composition A.sub.2-w-xA'.sub.wA''.sub.xB.sub.2-y-zB'.sub.yB''.sub.zO.sub.7-.DELTA.. Distribution of catalytically active metals throughout the structure at the B site creates an active and well dispersed metal locked into place in the crystal structure. This greatly reduces the metal sintering that typically occurs on supported catalysts used in reforming reactions, and reduces deactivation by sulfur and carbon. Further, oxygen mobility may also be enhanced by elemental exchange of promoters at sites in the pyrochlore. The pyrochlore catalyst material may be utilized in catalytic reforming reactions for the conversion of hydrocarbon fuels into synthesis gas (H.sub.2+CO) for fuel cells, among other uses.

Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

DEFF Research Database (Denmark)

Beier, Matthias Josef

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

High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons

International Nuclear Information System (INIS)

Perez, M.; Gonzalez, D.

1988-01-01

A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs

Hydrocarbon pollution from marinas in estuarine sediments

Science.gov (United States)

Voudrias, Evangelos A.; Smith, Craig L.

1986-03-01

A measure of the impact of marinas on three Eastern Virginia estuarine creeks was obtained by a study of hydrocarbons in their sediments. Two of the creeks support considerable marine activity, including pleasure boat marinas, boat repair facilities, and commercial fishing operations. The third creek, which served as a control, is seldom used by boats, and is surrounded by marsh and woodland. Sediments from the creeks with marinas contained significantly higher levels of both aromatic and aliphatic hydrocarbons than did the control. Differences in the concentrations of certain oil-pollution indicators, such as the 17α,21β-hopane homologs and phytane, and low molecular weight aromatic hydrocarbons, are indicative of light petroleum fractions. Most of the aromatic hydrocarbons from all creeks, however, appear to have a pyrogenic origin. Although hydrocarbons from three probable origins (petroleum, pyrogenesis, and recent biosynthesis) were detected in all locations, the petroleum-derived and pyrogenic hydrocarbons were of only minor importance relative to the biogenic hydrocarbons in the control creek.

BIOREMEDIATION OF A PETROLEUM-HYDROCARBON

African Journals Online (AJOL)

ES OBE

under field conditions in the bioremediation of a petroleum- hydrocarbon polluted ... an accelerated biodegradation of petroleum hydrocarbons in a polluted agricultural soil ..... 12) Jackson, M.L. Soil chemical analysis. ... biological assay. 3 rd.

Formation of nitro products from the gas-phase OH radical-initiated reactions of toluene, naphthalene, and biphenyl: effect of NO2 concentration.

Science.gov (United States)

Nishino, Noriko; Atkinson, Roger; Arey, Janet

2008-12-15

Aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs), are released into the atmosphere principally during incomplete combustion and account for approximately 20% of nonmethane organic compounds in urban air. Reaction with OH radicals is the dominant atmospheric chemical loss process for aromatic hydrocarbons, leading mainly to the formation of an OH-aromatic or OH-PAH adduct which then reacts with O2 and/or NO2. For OH-monocyclic aromatic adducts, reaction with O2 dominates under atmospheric conditions; however, no data are available concerning the relative importance of reactions of OH-PAH adducts with O2 and NO2. We have measured formation yields of 3-nitrotoluene, 1- and 2-nitronaphthalene, and 3-nitrobiphenyl from the OH radical-initiated reactions of toluene, naphthalene, and biphenyl as a function of NO2 concentration. Our data showthatthe OH-aromatic adduct reactions with O2 and NO2 are of equal importance in the atmosphere at NO2 mixing ratios of approximately 3.3 ppmV for toluene, approximately 0.06 ppmV for naphthalene, and approximately 0.6 ppmV for biphenyl. Ambient concentrations of toluene, naphthalene, and biphenyl and their nitrated products measured at a site in the Los Angeles air basin are consistent with our laboratory measurements.

Aliphatic hydrocarbon and polycyclic aromatic hydrocarbon geochemistry of twelve major rivers in the Northwest Territories

International Nuclear Information System (INIS)

Backus, S.; Swyripa, M.; Peddle, J.; Jeffries, D.S.

1995-01-01

Suspended sediment and water samples collected from twelve major rivers in the Northwest Territories were analyzed for aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) to assess the sources and transport of hydrocarbons entering the Arctic Ocean. Three stations on the Mackenzie River and one station near the mouth of eleven other northern rivers were selected for sampling. Samples were collected on the Mackenzie River on four occasions to characterize spring, summer and fall flow conditions and once on the remaining eleven rivers during high flow conditions. The Mackenzie River is distinctively different then the other eleven rivers. Naturally occurring hydrocarbons predominate in the river. These hydrocarbons include biogenic alkanes, diagenic PAHs, petrogenic alkanes, and PAHs from oil seeps and/or bitumens. Anthropogenic inputs of PAHs are low as indicated by low concentrations of combustion PAHs. Alkyl PAH distributions indicate that a significant component of the lower molecular weight PAH fraction is petrogenic. The majority of the high molecular weight PAHs, together with the petrogenic PAHs have a principal source in the Mackenzie River

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.

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).

Characteristics of atmospheric non-methane hydrocarbons during haze episode in Beijing, China.

Science.gov (United States)

Guo, Songjun; Tan, Jihua; Duan, Jingchun; Ma, Yongliang; Yang, Fumo; He, Kebin; Hao, Jimin

2012-12-01

This study firstly focused on non-methane hydrocarbons (NMHCs) during three successive days with haze episode (16-18 August 2006) in Beijing. Concentrations of alkanes, alkenes, aromatic hydrocarbons, and ethyne all peaked at traffic rush hour, implying vehicular emission; and alkanes also peaked at non-traffic rush hour in the daytime, implying additional source. Especially, alkanes and aromatics clearly showed higher levels in the nighttime than that in the daytime, implying their active photochemical reactions in the daytime. Correlation coefficients (R (2)) showed that propane, n-butane, i-butane, ethene, propene, and benzene correlated with ethyne (R (2) = 0.61-0.66), suggesting that their main source is vehicular emission; 2-methylpentane and n-hexane correlated with i-pentane (R (2) = 0.61-0.64), suggesting that gasoline evaporation is their main source; and ethylbezene, m-/p-xylene, and o-xylene correlated with toluene (R (2) = 0.60-0.79), suggesting that their main source is similar to that of toluene (e.g., solvent usage). The R (2) of ethyne, i-pentane, and toluene with total NMHCs were 0.58, 0.76, and 0.60, respectively, indicating that ambient hydrocarbons are associated with vehicular emission, gasoline evaporation, and solvent usage. The sources of other hydrocarbons (e.g., ethane) might be natural gas leakage, biogenic emission, or long-range transport of air pollutants. Measured higher mean B/T ratio (0.78 ± 0.27) was caused by the more intensive photochemical activity of toluene than benzene, still indicating the dominant emission from vehicles.

Ion cyclotron resonance study of reactions of ions with hydrogen atoms

International Nuclear Information System (INIS)

Karpas, Z.; Anicich, V.; Huntress, W.T. Jr.

1979-01-01

Reactions of H 2 + , HeH + , and CO 2 + ions with hydrogen atoms, and the reactions of D 2 + , CO 2 + , CO + , N 2 + and HCN + with deuterium atoms, were studied using ion cyclotron resonance techniques. These reactions proceed predominantly via a charge transfer mechanism. The rate constants measured are: 6.4, 9.1, 1.1, 5.0, 0.84, 0.90, 1.2, and 0.37 x 10 -10 cm 3 /sec, respectively. Hydrocarbon ions of the types CH/sub n/ + and C 2 H/sub n/ + , where n=2--4, do not react with H or D atoms

Application of numerical modeling of selective NOx reduction by hydrocarbon under diesel transient conditions in consideration of hydrocarbon adsorption and desorption process

International Nuclear Information System (INIS)

Watanabe, Y.; Asano, A.; Banno, K.; Yokota, K.; Sugiura, M.

2001-01-01

A model of NO x selective reduction by hydrocarbon (HC) was developed, which takes into account the adsorption and desorption of HC. The model was applied for predicting the performance of a De-NO x catalytic reactor, working under transient conditions such as a legislative driving cycle. Diesel fuel was used as a supplemental reductant. The behavior of HC and NO x reactions and HC adsorption and desorption has been simulated successfully by our numerical approach under the transient conditions of the simulated Japanese 10-15 driving cycle. Our model is expected to optimize the design of selective diesel NO x reduction systems using a diesel fuel as a supplemental reductant

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

Science.gov (United States)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

Emerging conservation challenges and prospects in an era of offshore hydrocarbon exploration and exploitation.

Science.gov (United States)

Kark, Salit; Brokovich, Eran; Mazor, Tessa; Levin, Noam

2015-12-01

Globally, extensive marine areas important for biodiversity conservation and ecosystem functioning are undergoing exploration and extraction of oil and natural gas resources. Such operations are expanding to previously inaccessible deep waters and other frontier regions, while conservation-related legislation and planning is often lacking. Conservation challenges arising from offshore hydrocarbon development are wide-ranging. These challenges include threats to ecosystems and marine species from oil spills, negative impacts on native biodiversity from invasive species colonizing drilling infrastructure, and increased political conflicts that can delay conservation actions. With mounting offshore operations, conservationists need to urgently consider some possible opportunities that could be leveraged for conservation. Leveraging options, as part of multi-billion dollar marine hydrocarbon operations, include the use of facilities and costly equipment of the deep and ultra-deep hydrocarbon industry for deep-sea conservation research and monitoring and establishing new conservation research, practice, and monitoring funds and environmental offsetting schemes. The conservation community, including conservation scientists, should become more involved in the earliest planning and exploration phases and remain involved throughout the operations so as to influence decision making and promote continuous monitoring of biodiversity and ecosystems. A prompt response by conservation professionals to offshore oil and gas developments can mitigate impacts of future decisions and actions of the industry and governments. New environmental decision support tools can be used to explicitly incorporate the impacts of hydrocarbon operations on biodiversity into marine spatial and conservation plans and thus allow for optimum trade-offs among multiple objectives, costs, and risks. © 2015 Society for Conservation Biology.

A disposable electrochemical immunosensor for prolactin involving affinity reaction on streptavidin-functionalized magnetic particles

International Nuclear Information System (INIS)

Moreno-Guzman, Maria; Gonzalez-Cortes, Araceli; Yanez-Sedeno, Paloma; Pingarron, Jose M.

2011-01-01

A novel electrochemical immunosensor was developed for the determination of the hormone prolactin. The design involved the use of screen-printed carbon electrodes and streptavidin-functionalized magnetic particles. Biotinylated anti-prolactin antibodies were immobilized onto the functionalized magnetic particles and a sandwich-type immunoassay involving prolactin and anti-prolactin antibody labelled with alkaline phosphatase was employed. The resulting bio-conjugate was trapped on the surface of the screen-printed electrode with a small magnet and prolactin quantification was accomplished by differential pulse voltammetry of 1-naphtol formed in the enzyme reaction using 1-naphtyl phosphate as alkaline phosphatase substrate. All variables involved in the preparation of the immunosensor and in the electrochemical detection step were optimized. The calibration plot for prolactin exhibited a linear range between 10 and 2000 ng mL -1 with a slope value of 7.0 nA mL ng -1 . The limit of detection was 3.74 ng mL -1 . Furthermore, the modified magnetic beads-antiprolactin conjugates showed an excellent stability. The immunosensor exhibited also a high selectivity with respect to other hormones. The analytical usefulness of the immnunosensor was demonstrated by analyzing human sera spiked with prolactin at three different concentration levels.

A disposable electrochemical immunosensor for prolactin involving affinity reaction on streptavidin-functionalized magnetic particles

Energy Technology Data Exchange (ETDEWEB)

Moreno-Guzman, Maria; Gonzalez-Cortes, Araceli [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain); Yanez-Sedeno, Paloma, E-mail: yseo@quim.ucm.es [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain); Pingarron, Jose M. [Department of Analytical Chemistry, Faculty of Chemistry, University Computense of Madrid, 28040 Madrid (Spain)

2011-04-29

A novel electrochemical immunosensor was developed for the determination of the hormone prolactin. The design involved the use of screen-printed carbon electrodes and streptavidin-functionalized magnetic particles. Biotinylated anti-prolactin antibodies were immobilized onto the functionalized magnetic particles and a sandwich-type immunoassay involving prolactin and anti-prolactin antibody labelled with alkaline phosphatase was employed. The resulting bio-conjugate was trapped on the surface of the screen-printed electrode with a small magnet and prolactin quantification was accomplished by differential pulse voltammetry of 1-naphtol formed in the enzyme reaction using 1-naphtyl phosphate as alkaline phosphatase substrate. All variables involved in the preparation of the immunosensor and in the electrochemical detection step were optimized. The calibration plot for prolactin exhibited a linear range between 10 and 2000 ng mL{sup -1} with a slope value of 7.0 nA mL ng{sup -1}. The limit of detection was 3.74 ng mL{sup -1}. Furthermore, the modified magnetic beads-antiprolactin conjugates showed an excellent stability. The immunosensor exhibited also a high selectivity with respect to other hormones. The analytical usefulness of the immnunosensor was demonstrated by analyzing human sera spiked with prolactin at three different concentration levels.

Cross sections and reaction rates of d+{sup 8}Li reactions involved in Big Bang nucleosynthesis

Energy Technology Data Exchange (ETDEWEB)

Balbes, M.J. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Farrell, M.M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Boyd, R.N. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics]|[Department of Astronomy, Ohio State University, Columbus, OH 43210 (United States); Gu, X. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Hencheck, M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kalen, J.D. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Mitchell, C.A. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kolata, J.J. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Lamkin, K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Smith, R. [Division of Nuclear Medicine, Department of Radiology, Hospital of the University of Pennsylvania, Philadelphia, PA 19104 (United States); Tighe, R. [Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Ashktorab, K. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Becchetti, F.D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Brown, J. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Roberts, D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Wang, T.F. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Humphrey, D. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Vourvopoulos, G. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Islam, M.S. [Department of Physics, Ball State University, Muncie, IN 47306 (United States)

1995-02-20

We have measured angular distributions of the {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H and {sup 2}H({sup 8}Li, {sup 9}Be)n reactions at E{sub c.m.}=1.5 to 2.8 MeV using an {sup 8}Li-radioactive-beam technique. Astrophysical S-factors and reaction rates were calculated from the measured cross sections. Although the {sup 2}H({sup 8}Li, {sup 9}Be)n cross section is small, it can contribute to {sup 9}Be synthesis. The {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H reaction has a sufficiently large cross section to destroy {sup 8}Li, which may decrease the synthesis of heavier elements. No products from the {sup 2}H({sup 8}Li, {sup 9}Li)p reaction were detected. We also present the results of calculations using the inhomogeneous model of primordial nucleosynthesis in several regions of parameter space. ((orig.))

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

Energy Technology Data Exchange (ETDEWEB)

Tan, E. C. D.; Talmadge, M.; Dutta, A.; Hensley, J.; Schaidle, J.; Biddy, M.; Humbird, D.; Snowden-Swan, L. J.; Ross, J.; Sexton, D.; Yap, R.; Lukas, J.

2015-03-01

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

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

Science.gov (United States)

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

2013-01-01

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

Process for separating liquid hydrocarbons from waxes

Energy Technology Data Exchange (ETDEWEB)

Sowa, F J

1948-03-08

A process is described for the separation of liquid hydrocarbons from waxes comprising adding to a mixture of liquid hydrocarbons and waxes a sufficient quantity of an organo-silicon compound to cause the separation of the hydrocarbon and wax. The organo-silicon compounds are selected from the class of organic silicanes and their hydrolysis products and polymers. The silicanes have the formula R/sub y/SiX/sub z/, in which R is a saturated or unsaturated hydrocarbon radical, X is a halogen or another hydrocarbon radical or an -OR group, y has a value 1, 2, or 3 and z has a value 1, 2, or 3.

Conversion of Dimethyl Ether to Branched Hydrocarbons Over Cu/BEA: the Roles of Lewis Acidic and Metallic Sites in H2 Incorporation

Energy Technology Data Exchange (ETDEWEB)

Hensley, Jesse E.; Schaidle, Joshua A.; Ruddy, Daniel A.; Cheah, Singfoong; Habas, Susan E.; Pan, Ming; Zhang, Guanghui; Miller, Jeffrey T.

2017-04-26

Conversion of biomass to fuels remains as one of the most promising approach to support our energy needs. It has been previously shown that the gasification of non-edible cellulosic biomass can be used to derive fuels like methanol and dimethyl ether (DME). However, the use of methanol and DME is limited due to the fact that they have low energy densities, poor lubricity and lower viscosity when compared to long-chain hydrocarbons. Increasing the blending percentage can also lead to undesired amounts of oxygenated molecules in the transportation fuel infrastructure, which restrict their applicability as jet or diesel fuels. Consequently, the petroleum-derived hydrocarbons remain as the main constituent of the middle-distillate based fuels. One way to increase the share of biofuels in middle-distillates is to use methanol/DME as building blocks for producing renewable, energy-dense hydrocarbons. One way to achieve this is by catalytically converting the DME and methanol to light olefins, followed by oligomerization to higher molecular weight premium alkanes, which can directly be used as kerosene/diesel fuels. Here, we report the catalytic dimerization of biomass-derived deoxygenated olefins into transportation fuel-range hydrocarbons under liquid-phase stirred-batch conditions. Specifically, the effect of operating conditions, such as reaction temperature, solvent-type, reaction duration and olefin-structure, on the conversion, selectivity and kinetics of dimerization of triptene (2,3,3-trimethyl-1-butene) were investigated. Triptene, as previously reported, is one of the major products of DME-homologation reaction over a BEA zeolite4. We show that triptene can be converted to high quality middle-distillates using a commercially available ion-exchange acid resin, Amberlyst-35 (dry) by the process of catalytic dimerization.

[Simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter by gas chromatography-tandem mass spectrometry].

Science.gov (United States)

Zhang, Xiaotao; Zhang, Li; Ruan, Yibin; Wang, Weiwei; Ji, Houwei; Wan, Qiang; Lin, Fucheng; Liu, Jian

2017-10-08

A method for the simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter was developed by isotope internal standard combined with gas chromatography-tandem mass spectrometry. The cigarette filters were extracted with dichloromethane, and the extract was filtered with 0.22 μm organic phase membrane. The samples were isolated by DB-5MS column (30 m×0.25 mm, 0.25 μm) and detected using multiple reaction monitoring mode of electron impact source under positive ion mode. The linearities of the 15 polycyclic aromatic hydrocarbons (acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, ben[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenzo[ a,h ]anthracene, benzo[ g,h,i ]perylene and indeno[1,2,3- c,d ]pyrene) were good, and the correlation coefficients ( R 2 ) ranged from 0.9914 to 0.9999. The average recoveries of the 15 polycyclic aromatic hydrocarbons were 81.6%-109.6% at low, middle and high spiked levels, and the relative standard deviations were less than 16%, except that the relative standard deviation of fluorene at the low spiked level was 19.2%. The limits of detection of the 15 polycyclic aromatic hydrocarbons were 0.02 to 0.24 ng/filter, and the limits of quantification were 0.04 to 0.80 ng/filter. The method is simple, rapid, accurate, sensitive and reproducible. It is suitable for the quantitative analysis of the 15 polycyclic aromatic hydrocarbons in cigarette filters.

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-10-15

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

Hydrocarbon-soluble calcium hydride: a "worker-bee" in calcium chemistry.

Science.gov (United States)

Spielmann, Jan; Harder, Sjoerd

2007-01-01

The reactivity of the hydrocarbon-soluble calcium hydride complex [{CaH(dipp-nacnac)(thf)}(2)] (1; dipp-nacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with a large variety of substrates has been investigated. Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes. Similarly, reduction of the C[triple chemical bond]N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)R}(dipp-nacnac)] and [Ca{C(H)=NR}(dipp-nacnac)], respectively. Complexation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs. In reaction with epoxides, nucleophilic ring-opening is observed as the major reaction. The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH(2), which is essentially inert and is used as a common drying agent. Crystal structures of the following products are presented: [{Ca{OC(H)Ph(2)}(dipp-nacnac)}(2)], [{Ca{N=C(H)Ph}(dipp-nacnac)}(2)], [{Ca{C(H)=NC(Me)(2)CH(2)C(Me)(3)}(dipp-nacnac)}(2)], [{Ca{C(H)=NCy}(dipp-nacnac)}(2)], [Ca(dipp-nacnac)(thf)](+)[H(2)BC(8)H(14)](-) and [{Ca(OCy)(dipp-nacnac)}(2)]. The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.

Comparative Genomics of the Ubiquitous, Hydrocarbon-degrading Genus Marinobacter

Science.gov (United States)

Singer, E.; Webb, E.; Edwards, K. J.

2012-12-01

The genus Marinobacter is amongst the most ubiquitous in the global oceans and strains have been isolated from a wide variety of marine environments, including offshore oil-well heads, coastal thermal springs, Antarctic sea water, saline soils and associations with diatoms and dinoflagellates. Many strains have been recognized to be important hydrocarbon degraders in various marine habitats presenting sometimes extreme pH or salinity conditions. Analysis of the genome of M. aquaeolei revealed enormous adaptation versatility with an assortment of strategies for carbon and energy acquisition, sensation, and defense. In an effort to elucidate the ecological and biogeochemical significance of the Marinobacters, seven Marinobacter strains from diverse environments were included in a comparative genomics study. Genomes were screened for metabolic and adaptation potential to elucidate the strategies responsible for the omnipresence of the Marinobacter genus and their remedial action potential in hydrocarbon-polluted waters. The core genome predominantly encodes for key genes involved in hydrocarbon degradation, biofilm-relevant processes, including utilization of external DNA, halotolerance, as well as defense mechanisms against heavy metals, antibiotics, and toxins. All Marinobacter strains were observed to degrade a wide spectrum of hydrocarbon species, including aliphatic, polycyclic aromatic as well as acyclic isoprenoid compounds. Various genes predicted to facilitate hydrocarbon degradation, e.g. alkane 1-monooxygenase, appear to have originated from lateral gene transfer as they are located on gene clusters of 10-20% lower GC-content compared to genome averages and are flanked by transposases. Top ortholog hits are found in other hydrocarbon degrading organisms, e.g. Alcanivorax borkumensis. Strategies for hydrocarbon uptake encoded by various Marinobacter strains include cell surface hydrophobicity adaptation via capsular polysaccharide biosynthesis and attachment

Selected ion flow tube studies of S2+ reactions with a series of organic molecules

Science.gov (United States)

Decker, Brian K.; Adams, Nigel G.

1997-11-01

A selected ion flow tube (SIFT) has been used to study the reactions of S2+ with a series of organic molecules (as well as H2, CO, NH3, NO and NO2). These include the hydrocarbons, C2H4, C2H6, CH2CCH2, CH3CHCH2 and C3H8; alcohols and thiols, CH3OH, C2H5OH, CH3SH and C2H5SH; ethers (CH3)2O and (C2H5)2O; aldehydes and ketones, CH3CHO, C2H5CHO and (CH3)2CO; and carboxylic acids and esters, HCO2H, HCO2CH3, HCO2C2H5, CH3CO2H, CH3CO2CH3, CH3CO2C2H5, C2H5CO2H, C2H5CO2CH3 and C2H5CO2C2H5. The rate coefficients are generally close to the collisional values, with exceptions among the reactions involving the smaller molecules. Most prevalent are abstraction reactions leading to formation of the thiosulfeno radical, HS2, or its protonated form; three-body associations; and channels leading to formation of the acetyl and propionyl cations, CH3CO+ and C2H5CO+, respectively. Only in reactions involving the alkenes is cleavage of the S---S bond of S2+ observed. The isomeric molecules in the data set generally react very differently, as would be expected from reactivity controlled by the position and complexity of the functional groups. The data are discussed in terms of reaction mechanisms, thermodynamics, and implications for interstellar chemistry.

An investigation of molybdenum and molybdenum oxide catalyzed hydrocarbon formation reactions

Energy Technology Data Exchange (ETDEWEB)

Tysoe, W.T.

1995-09-01

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

F/Cl + C2H2 reactions: Are the addition and hydrogen abstraction direct processes?

International Nuclear Information System (INIS)

Li Jilai; Geng Caiyun; Huang Xuri; Zhan Jinhui; Sun Chiachung

2006-01-01

The reactions of atomic radical F and Cl with acetylene have been studied theoretically using ab initio quantum chemistry methods and transition state theory. The doublet potential energy surfaces were calculated at the CCSD(T)/aug-cc-pVDZ//CCSD/6-31G(d,p), CCSD(T)/aug-cc-pVDZ//UMP2/6-311++G(d,p) and compound method Gaussian-3 levels. Two reaction mechanisms including the addition-elimination and the hydrogen abstraction reaction mechanisms are considered. In the addition-elimination reactions, the halogen atoms approach C 2 H 2 , perpendicular to the C≡C triple bond, forming the pre-reactive complex C1 at the reaction entrance. C1 transforms to intermediate isomer I1 via transition state TSC1/1 with a negative/small barrier for C 2 H 2 F/C 2 H 2 Cl system, which can proceed by further eliminating H atom endothermally. While the hydrogen abstraction reactions also involve C1 for the fluorine atom abstraction of hydrogen, yet the hydrogen abstraction by chlorine atom first forms a collinear hydrogen-bonded complex C2. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. According to our results, the presence of pre-reactive complexes indicates that the simple hydrogen abstraction and addition in the halogen atoms reaction with unsaturated hydrocarbon should be more complex. Furthermore, based on the analysis of the kinetics of all channels through which the addition and abstraction reactions proceed, we expect that the actual feasibility of the reaction channels may depend on the reaction conditions in the experiment. The present study may be helpful for probing the mechanisms of the title reactions and understanding the halogen chemistry

Gamma-radiation induced polymerization of methyl methacrylate in aliphatic hydrocarbons: kinetics and evidence for incorporation of hydrocarbon in the polymer chain

International Nuclear Information System (INIS)

Mohan, H.; Iyer, R.M.

1989-01-01

On γ-radiolysis, the rate of polymerization of methyl methacrylate in hydrocarbon solvents is observed to decrease. It is explained by hydrocarbon entry into the polymer chains. The hydrocarbon entry into the polymer chains is observed to take place at later stages of polymerization and increases with hydrocarbon chain length. The extent of hydrocarbon entry into the polymer chains is estimated by NMR and GLC analysis. It is observed to be equal to ∼ 12% corresponding to ∼ 97 hexadecane molecules in each polymer chain. The IR, DSC, MW determination and radiation effects on the polymer showed evidences for hydrocarbon entry into the polymer. It is explained by chain transfer from the growing polymer radical to the hydrocarbon molecules. The chain transfer constant is determined to be equal to 1 x 10 -2 . (author)

Stability and isomerization reactions of phenyl cation C{sub 6}H{sub 5}{sup +} isomers

Energy Technology Data Exchange (ETDEWEB)

Shi, Dandan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yang, Xue [College of Science, Jilin Institute of Chemical Technology, Jilin 132022 (China); Zhang, Xiaomei; Shan, Shimin [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Xu, Haifeng, E-mail: xuhf@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yan, Bing, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China)

2016-03-01

Highlights: • A total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations were obtained at density functional theory. • The stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers were performed. • The structures, frequencies, thermodynamic properties of isomers were summarized. • Ring to ring or chain isomerization pathways were investigated using IRC method. • Result shows reactions contain hydrogen transfer, bond broken and reconstruction. - Abstract: As a key polyatomic molecular cation that plays a pivotal role in growth of the polycyclic aromatic hydrocarbons, phenyl cation C{sub 6}H{sub 5}{sup +} exhibits various isomers and isomerization reactions. Investigation on the structure and stability of the isomers as well as the isomerization is important for better understanding the chemical reactions involving C{sub 6}H{sub 5}{sup +} cations. In this work, we have performed a theoretical study on the stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers at density functional theory B3LYP/6-311G (d, p) level. We have obtained a total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations, most of which are reported for the first time. The geometries, vibrational frequencies, thermodynamic properties and stability of 28 out of 60 isomers have been summarized in detail. Different ring-to-ring and ring-to-chain isomerization pathways, which are connected via 28 transition states, have been investigated using the intrinsic reaction coordinate method. The results show that the isomerization reactions occur via hydrogen migration followed by bond-breaking and reconstruction.

Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

International Nuclear Information System (INIS)

Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don

2017-01-01

Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don [Department of Chemistry, University of California, Berkeley, CA (United States)

2017-04-18

Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Indirect Measurements for (p,α) Reactions Involving Boron Isotopes

International Nuclear Information System (INIS)

Lamia, L.; Spitaleri, C.; Romano, S.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Pizzone, R. G.; Puglia, S. M. R.; Sergi, M. L.; Tudisco, S.; Tumino, A.; Carlin, N.; Szanto, M. G. del; Liguori Neto, R.; Moura, M. M. de; Munhoz, M. G.; Souza, F. A.; Suaide, A. A. P.; Szanto, E.

2008-01-01

Light elements lithium, beryllium and boron (LiBeB) were used in the last years as 'possible probe' for a deeper understanding of some extra-mixing phenomena occurring in young Main-Sequence stars. They are mainly destroyed by (p,α) reactions and cross section measurements for such channels are then needed. The Trojan Horse Method (THM) allows one to extract the astrophysical S(E)-factor without the experience of tunneling through the Coulomb barrier. In this work a resume of the recent results about the 11 B(p,α 0 ) 8 Be and 10 B(p,α) 7 Be reactions is shown

Russia and China hydrocarbon relations. A building block toward international hydrocarbon regulation?

International Nuclear Information System (INIS)

Locatelli, Catherine; Abbas, Mehdi; Rossiaud, Sylvain

2015-12-01

This article is a first step of a research agenda on international hydrocarbon regulations. With regards to both: i) the new wealth and power equilibrium in the international political economy and ii) the new political economy of carbon that is emerging from The Paris agreement on Climate changes, this research agenda aims at analysing the changing national structures of governance and the ways these changes lead to international, bilateral, pluri-lateral or multilateral hydrocarbon regulation

Comparison of Atmospheric Pressure Chemical Ionization and Field Ionization Mass Spectrometry for the Analysis of Large Saturated Hydrocarbons.

Science.gov (United States)

Jin, Chunfen; Viidanoja, Jyrki; Li, Mingzhe; Zhang, Yuyang; Ikonen, Elias; Root, Andrew; Romanczyk, Mark; Manheim, Jeremy; Dziekonski, Eric; Kenttämaa, Hilkka I

2016-11-01

Direct infusion atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was compared to field ionization mass spectrometry (FI-MS) for the determination of hydrocarbon class distributions in lubricant base oils. When positive ion mode APCI with oxygen as the ion source gas was employed to ionize saturated hydrocarbon model compounds (M) in hexane, only stable [M - H] + ions were produced. Ion-molecule reaction studies performed in a linear quadrupole ion trap suggested that fragment ions of ionized hexane can ionize saturated hydrocarbons via hydride abstraction with minimal fragmentation. Hence, APCI-MS shows potential as an alternative of FI-MS in lubricant base oil analysis. Indeed, the APCI-MS method gave similar average molecular weights and hydrocarbon class distributions as FI-MS for three lubricant base oils. However, the reproducibility of APCI-MS method was found to be substantially better than for FI-MS. The paraffinic content determined using the APCI-MS and FI-MS methods for the base oils was similar. The average number of carbons in paraffinic chains followed the same increasing trend from low viscosity to high viscosity base oils for the two methods.

Elucidation of the mechanism of conversion of methanol and ethanol to hydrocarbons on a new type of synthetic zeolite

NARCIS (Netherlands)

Derouane, E.G.; Nagy, J.B.; Dejaifve, P.; Hooff, van J.H.C.; Spekman, B.P.A.; Védrine, J.C.; Naccache, C.

1978-01-01

13C nuclear magnetic resonance and vapor-phase chromatography have been used to investigate the conversions of methanol and ethanol to hydrocarbons on a synthetic zeolite of the type H-ZSM-5 as described by Mobil. Methanol is first dehydrated to dimethyl ether and ethylene. Then the reaction

Oxygen-containing coke species in zeolite-catalyzed conversion of methanol to hydrocarbons

KAUST Repository

Liu, Zhaohui

2016-10-06

Zeolites are the most commonly used catalysts for methanol-to-hydrocarbon (MTH) conversion. Here, we identified two oxygen-containing compounds as coke species in zeolite catalysts after MTH reactions. We investigated the possible influences of the oxygen-containing compounds on coke formation, catalyst deactivation, product selectivity, and the induction period of the MTH reaction through a series of controlled experiments in which one of the identified compounds (2,3-dimethyl-2-cyclopenten-1-one) was co-fed with methanol over a zeolite H-ZSM-5 catalyst. Our results allow us to infer that once produced, the oxygen-containing compounds block the Brønsted acid sites by strong chemisorption and their rapid conversion to aromatics expedites the formation of coke and thus the deactivation of the catalyst. A minor effect of the production of such compounds during the MTH reaction is that the aromatic-based catalytic cycle can be slightly promoted to give higher selectivity to ethylene.

27 CFR 21.125 - Rubber hydrocarbon solvent.

Science.gov (United States)

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Rubber hydrocarbon solvent. 21.125 Section 21.125 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU....125 Rubber hydrocarbon solvent. (a) Rubber hydrocarbon solvent is a petroleum derivative. (b...

Development of an efficient bacterial consortium for the potential remediation of hydrocarbons from contaminated sites

Directory of Open Access Journals (Sweden)

Kaustuvmani Patowary

2016-07-01

Full Text Available The intrinsic biodegradability of hydrocarbons and the distribution of proficient degrading microorganisms in the environment are very crucial for the implementation of bioremediation practices. Among others, one of the most favorable methods that can enhance the effectiveness of bioremediation of hydrocarbon-contaminated environment is the application of biosurfactant producing microbes. In the present study, the biodegradation capacities of native bacterial consortia towards total petroleum hydrocarbons (TPH with special emphasis to poly aromatic hydrocarbons (PAHs were determined. The purpose of the study was to isolate TPH degrading bacterial strains from various petroleum contaminated soil of Assam, India and develop a robust bacterial consortium for bioremediation of crude oil of this native land. From a total of 23 bacterial isolates obtained from three different hydrocarbons contaminated samples 5 isolates, namely KS2, PG1, PG5, R1 and R2 were selected as efficient crude oil degraders with respect to their growth on crude oil enriched samples. Isolates KS2, PG1 and R2 are biosurfactant producers and PG5, R1 are non-producers. Fourteen different consortia were designed involving both biosurfactant producing and non-producing isolates. Consortium 10, which comprises two Bacillus strains namely, Bacillus pumilus KS2 and Bacillus cereus R2 (identified by 16s rRNA sequencing has shown the best result in the desired degradation of crude oil. The consortium showed degradation up to 84.15% of total petroleum hydrocarbon (TPH after five weeks of incubation, as revealed from gravimetric analysis. FTIR (Fourier transform infrared and GCMS (Gas chromatography-mass spectrometer analyses were correlated with gravimetric data which reveals that the consortium has removed a wide range of petroleum hydrocarbons in comparison with abiotic control including different aliphatic and aromatic hydrocarbons.

Cuticular hydrocarbons as potential kin recognition cues in a subsocial spider

DEFF Research Database (Denmark)

Grinsted, Lena; Bilde, Trine; D'Ettorre, Patrizia

2011-01-01

of recognition cues in subsocial species can provide insights into evolutionary pathways leading to permanent sociality and kin-selected benefits of cooperation. In subsocial spiders, empirical evidence suggests the existence of both kin recognition and benefits of cooperating with kin, whereas the cues for kin...... recognition have yet to be identified. However, cuticular hydrocarbons have been proposed to be involved in regulation of tolerance and interattraction in spider sociality. Here, we show that subsocial Stegodyphus lineatus spiderlings have cuticular hydrocarbon profiles that are sibling-group specific, making...... be branched alkanes that are influenced very little by rearing conditions and may be genetically determined. This indicates that a specific group of cuticular chemicals, namely branched alkanes, could have evolved to act as social recognition cues in both insects and spiders....

A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

International Nuclear Information System (INIS)

Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

2014-01-01

The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

Process for desulfurizing hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1937-04-12

A process is described for the desulfurization of a mixture of hydrocarbons, and in particular hydrocarbons containing less than 7 atoms of carbon and sulfur compounds of the type of sulfur carbonyl, characterized by the fact that the mixture, preferably in the liquid phase, is brought in contact with a solution of caustic alkali, essentially anhydrous or preferably with a solution of alkali hydroxide in an organic hydroxy nonacid solvent, for example, an alcohol, or with an alkaline alcoholate, under conditions suitable to the formation of hydrogen sulfide which produces a hydrocarbon mixture free from sulfur compounds of the sulfur carbonyl type but containing hydrogen sulfide, and that it is treated, following mixing, having beem submitted to the first treatment, by means of aqueous alkaline hydroxide to eliminate the hydrogen sulfide.

Hydrocarbon-degrading bacteria isolation and surfactant influence ...

African Journals Online (AJOL)

Hydrocarbons are substantially insoluble in water, often remaining partitioned in the non-aqueous phase liquid (NAPL). However, there had been little or no attempts to advance the bioavailability of hydrocarbons through the use of surfactants. This study was conducted based on the need to isolate hydrocarbon degrading ...

Sensitivity ranking for freshwater invertebrates towards hydrocarbon contaminants.

Science.gov (United States)

Gerner, Nadine V; Cailleaud, Kevin; Bassères, Anne; Liess, Matthias; Beketov, Mikhail A

2017-11-01

Hydrocarbons have an utmost economical importance but may also cause substantial ecological impacts due to accidents or inadequate transportation and use. Currently, freshwater biomonitoring methods lack an indicator that can unequivocally reflect the impacts caused by hydrocarbons while being independent from effects of other stressors. The aim of the present study was to develop a sensitivity ranking for freshwater invertebrates towards hydrocarbon contaminants, which can be used in hydrocarbon-specific bioindicators. We employed the Relative Sensitivity method and developed the sensitivity ranking S hydrocarbons based on literature ecotoxicological data supplemented with rapid and mesocosm test results. A first validation of the sensitivity ranking based on an earlier field study has been conducted and revealed the S hydrocarbons ranking to be promising for application in sensitivity based indicators. Thus, the first results indicate that the ranking can serve as the core component of future hydrocarbon-specific and sensitivity trait based bioindicators.

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

Directory of Open Access Journals (Sweden)

X. Xu

2003-01-01

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

Quadrupole type mass spectrometric study of the abstraction reaction between hydrogen atoms and ethane.

Science.gov (United States)

Bayrakçeken, Fuat

2008-02-01

The reactions of photochemically generated deuterium atoms of selected initial translational energy with ethane have been investigated. At each initial energy the relative probability of the atoms undergoing reaction or energy loss on collision with ethane was investigated, and the phenomenological threshold energy was measured as 30+/-5kJmol(-1) for the abstraction from the secondary C-H bonds. The ratio of relative yields per bond, secondary:primary was approximately 3 at the higher energies studied. The correlation of threshold energies with bond dissociation energies, heats of reaction and activation energies is discussed for abstraction reactions with several hydrocarbons.

Direct production of fractionated and upgraded hydrocarbon fuels from biomass

Science.gov (United States)

Felix, Larry G.; Linck, Martin B.; Marker, Terry L.; Roberts, Michael J.

2014-08-26

Multistage processing of biomass to produce at least two separate fungible fuel streams, one dominated by gasoline boiling-point range liquids and the other by diesel boiling-point range liquids. The processing involves hydrotreating the biomass to produce a hydrotreatment product including a deoxygenated hydrocarbon product of gasoline and diesel boiling materials, followed by separating each of the gasoline and diesel boiling materials from the hydrotreatment product and each other.

High Pressure Preignition Chemistry of Hydrocarbons and Hydrocarbon Mixtures

National Research Council Canada - National Science Library

Cernansky, N.P

1998-01-01

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

Contrasting the Community Structure of Arbuscular Mycorrhizal Fungi from Hydrocarbon-Contaminated and Uncontaminated Soils following Willow (Salix spp. L.) Planting

OpenAIRE

Hassan, Saad El-Din; Bell, Terrence H.; Stefani, Franck O. P.; Denis, David; Hijri, Mohamed; St-Arnaud, Marc

2014-01-01

Phytoremediation is a potentially inexpensive alternative to chemical treatment of hydrocarbon-contaminated soils, but its success depends heavily on identifying factors that govern the success of root-associated microorganisms involved in hydrocarbon degradation and plant growth stimulation. Arbuscular mycorrhizal fungi (AMF) form symbioses with many terrestrial plants, and are known to stimulate plant growth, although both species identity and the environment influence this relationship. Al...

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

Science.gov (United States)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

Process for refining hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Risenfeld, E H

1924-11-26

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

Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite

International Nuclear Information System (INIS)

Antos, G.J.

1981-01-01

Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of an iron component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, iron component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 4 wt. % iron and about 0.1 to about 5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of an iron component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e., platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the attenuated superactive multimetallic catalytic composite at reforming conditions

Synthesis of Biokerosene through Electrochemical Hydrogenation of Terpene Hydrocarbons from Turpentine Oil

Directory of Open Access Journals (Sweden)

Tedi Hudaya

2016-12-01

Full Text Available Indonesia possesses great potential for developing renewable resources as alternative fuels. For example, turpentine oil obtained from Pinus merkusii, which contains mostly monoterpene hydrocarbons (C10H16. The oil is highly suitable to be processed for biokerosene or even jet biofuel. It consists of hydrocarbons within the range of C10 to C15. However, it contains insufficient H and thus needs to be upgraded. In the present work, electrochemical hydrogenation was used for upgrading. In the electrochemical cell, stainless steel, silver, and carbon were used alternately for the anode, while copper and silver Raschig rings were used for the cathode. An electrolyte solution of cuprous ammonium formate was utilized not only as a source of H but also to draw the unsaturated hydrocarbons into the aqueous phase. The electrolyte : oil ratio (up to 2:1, electrolyte concentration (between 0.4 and 2 M and reaction time were varied throughout the experiments. The bromine number (unsaturation level of the turpentine oil, which was initially 1,86 (mole Br2/mole, was lowered significantly to 0.69-0.90. Promising increase of smoke point values were observed from 11 mm to 16-24 mm, indicating a higher H content of the processed oil, thus making it suitable as a substitute for petroleum kerosene.

Two-stage Catalytic Reduction of NOx with Hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

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

2005-12-21

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

Chemical fingerprinting of hydrocarbon-contamination in soil

DEFF Research Database (Denmark)

Boll, Esther Sørensen; Nejrup, Jens; Jensen, Julie K.

2015-01-01

Chemical fingerprinting analyses of 29 hydrocarbon-contaminated soils were performed to assess the soil quality and determine the main contaminant sources. The results were compared to an assessment based on concentrations of the 16 priority polycyclic aromatic hydrocarbons pointed out by the U...... and in assessing weathering trends of hydrocarbon contamination in the soils. Multivariate data analysis of sum-normalized concentrations could as a stand-alone tool distinguish between hydrocarbon sources of petrogenic and pyrogenic origin, differentiate within petrogenic sources, and detect weathering trends....... Diagnostic ratios of PACs were not successful for source identification of the heavily weathered hydrocarbon sources in the soils. The fingerprinting of contaminated soils revealed an underestimation of PACs in petrogenic contaminated soils when the assessment was based solely on EPAPAH16. As alkyl...

Air-dust-borne associations of phototrophic and hydrocarbon-utilizing microorganisms: promising consortia in volatile hydrocarbon bioremediation.

Science.gov (United States)

Al-Bader, Dhia; Eliyas, Mohamed; Rayan, Rihab; Radwan, Samir

2012-11-01

Aquatic and terrestrial associations of phototrophic and heterotrophic microorganisms active in hydrocarbon bioremediation have been described earlier. The question arises: do similar consortia also occur in the atmosphere? Dust samples at the height of 15 m were collected from Kuwait City air, and analyzed microbiologically for phototrophic and heterotrophic hydrocarbon-utilizing microorganisms, which were subsequently characterized according to their 16S rRNA gene sequences. The hydrocarbon utilization potential of the heterotrophs alone, and in association with the phototrophic partners, was measured quantitatively. The chlorophyte Gloeotila sp. and the two cyanobacteria Nostoc commune and Leptolyngbya thermalis were found associated with dust, and (for comparison) the cynobacteria Leptolyngbya sp. and Acaryochloris sp. were isolated from coastal water. All phototrophic cultures harbored oil vapor-utilizing bacteria in the magnitude of 10(5) g(-1). Each phototrophic culture had its unique oil-utilizing bacteria; however, the bacterial composition in Leptolyngbya cultures from air and water was similar. The hydrocarbon-utilizing bacteria were affiliated with Acinetobacter sp., Aeromonas caviae, Alcanivorax jadensis, Bacillus asahii, Bacillus pumilus, Marinobacter aquaeolei, Paenibacillus sp., and Stenotrophomonas maltophilia. The nonaxenic cultures, when used as inocula in batch cultures, attenuated crude oil in light and dark, and in the presence of antibiotics and absence of nitrogenous compounds. Aqueous and diethyl ether extracts from the phototrophic cultures enhanced the growth of the pertinent oil-utilizing bacteria in batch cultures, with oil vapor as a sole carbon source. It was concluded that the airborne microbial associations may be effective in bioremediating atmospheric hydrocarbon pollutants in situ. Like the aquatic and terrestrial habitats, the atmosphere contains dust-borne associations of phototrophic and heterotrophic hydrocarbon

Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

Science.gov (United States)

Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

2011-10-01

When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

Bioremediation: Technology for treating hydrocarbon-contaminated wastewater

Energy Technology Data Exchange (ETDEWEB)

Towprayoon, S.; Kuntrangwattana, S. [King Mongkut`s Institute of Technology, Bangkok (Thailand)

1996-12-31

Cutting oil wastewater from an iron and steel factory was applied to the soil windrow. Self-remediation was then compared with remediation with acclimatized indigenous microbes. The incremental reduction rate of the microorganisms and hydrocarbon-degradable microbes was slower in self-remediation than in the latter treatment. Within 30 days, when the acclimatized indigenous microbes were used, there was a significant reduction of the contaminated hydrocarbons, while self-remediation took longer to reduce to the same concentration. Various nitrogen sources were applied to the soil pile, namely, organic compost, chemical fertilizer, ammonium sulfate, and urea. The organic compost induced a high yield of hydrocarbon-degradable microorganisms, but the rate at which the cutting oil in the soil decreased was slower than when other nitrogen sources were used. The results of cutting oil degradation studied by gas chromatography showed the absence of some important hydrocarbons. The increment of the hydrocarbon-degradable microbes in the land treatment ecosystem does not necessarily correspond to the hydrocarbon reduction efficiency. 3 refs., 3 figs.

Zn-Mo/HZSM-5 Catalyst for Gasoil Range Hydrocarbon Production by Catalytic Hydrocracking of Ceiba pentandra oil

Directory of Open Access Journals (Sweden)

Yustia Wulandari Mirzayanti

2018-01-01

Full Text Available Biofuel from vegetable oil becomes one of the most suitable and logical alternatives to replace fossil fuel. The research focused on various metal ratio Zinc/Molybdenum/HZSM-5 (Zn-Mo/HZSM-5 catalyst to produce liquid hydrocarbon via catalytic hydrocracking of Ceiba penandra oil. The catalytic hydrocracking process has been applied in this study to crack Ceiba pentandra oil into a gasoil range hydrocarbon using Zn-Mo/HZSM-5 as a catalyst. The effect of various reaction temperature on the catalytic hydrocracking of Ceiba pentandra oil were studied. The Zn-Mo/HZSM-5 catalyst with metal ratio was prepared by incipient wetness impregnation method. This process used slurry pressure batch reactor with a mechanical stirrer. A series of experiments were carried out in the temperature range from 300-400 oC for 2 h at pressure between 10-15 bar. The conversion and selectivity were estimated. The liquid hydrocarbon product were identified to gasoline, kerosene, and gas oil. The results show that the use of Zn-Mo/HZSM-5 can produce gas oil as the most component in the product. Overall, the highest conversion and selectivity of gas oil range hydrocarbon was obtained when the ZnMo/HZSM-5 metal ratio was Zn(2.86 wt.%-Mo(5.32 wt.%/HZSM-5 and the name is Zn-Mo/HZSM-5_102. The highest conversion was obtained at 63.31 % and n-paraffin (gas oil range selectivity was obtained at 90.75 % at a temperature of 400 oC. Ceiba pentandra oil can be recommended as the source of inedible vegetable oil to produce gasoil as an environmentally friendly transportation fuel. Copyright © 2018 BCREC Group. All rights reserved Received: 8th September 2017; Revised: 9th September 2017; Accepted: 17th September 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Mirzayanti, Y.W., Kurniawansyah, F., Prajitno, D.H., Roesyadi, A. (2018. Zn-Mo/HZSM-5 Catalyst for Gasoil Range Hydrocarbon Production by Catalytic Hydrocracking of Ceiba pentandra

Preliminary Geospatial Analysis of Arctic Ocean Hydrocarbon Resources

Energy Technology Data Exchange (ETDEWEB)

Long, Philip E.; Wurstner, Signe K.; Sullivan, E. C.; Schaef, Herbert T.; Bradley, Donald J.

2008-10-01

Ice coverage of the Arctic Ocean is predicted to become thinner and to cover less area with time. The combination of more ice-free waters for exploration and navigation, along with increasing demand for hydrocarbons and improvements in technologies for the discovery and exploitation of new hydrocarbon resources have focused attention on the hydrocarbon potential of the Arctic Basin and its margins. The purpose of this document is to 1) summarize results of a review of published hydrocarbon resources in the Arctic, including both conventional oil and gas and methane hydrates and 2) develop a set of digital maps of the hydrocarbon potential of the Arctic Ocean. These maps can be combined with predictions of ice-free areas to enable estimates of the likely regions and sequence of hydrocarbon production development in the Arctic. In this report, conventional oil and gas resources are explicitly linked with potential gas hydrate resources. This has not been attempted previously and is particularly powerful as the likelihood of gas production from marine gas hydrates increases. Available or planned infrastructure, such as pipelines, combined with the geospatial distribution of hydrocarbons is a very strong determinant of the temporal-spatial development of Arctic hydrocarbon resources. Significant unknowns decrease the certainty of predictions for development of hydrocarbon resources. These include: 1) Areas in the Russian Arctic that are poorly mapped, 2) Disputed ownership: primarily the Lomonosov Ridge, 3) Lack of detailed information on gas hydrate distribution, and 4) Technical risk associated with the ability to extract methane gas from gas hydrates. Logistics may control areas of exploration more than hydrocarbon potential. Accessibility, established ownership, and leasing of exploration blocks may trump quality of source rock, reservoir, and size of target. With this in mind, the main areas that are likely to be explored first are the Bering Strait and Chukchi

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

International Nuclear Information System (INIS)

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

2007-01-01

Results of studies intended for the substantiation of a new energy-saving and safe technology for low cost hydrogen production have been presented. The technology's basis is direct mixing of water and (or) gaseous hydrocarbons with heavy liquid metal coolants (HLMC) Pb or Pb-Bi. Preliminary research has been done on thermal dynamics and kinetics of the processes taking place in the interaction of HLMC with hydrocarbon-containing gases. It has been shown as a result that water and gaseous hydrocarbons interact with molten Pb and Pb-Bi relatively quietly in chemical aspect (without ignition and explosions). Therefore, (and taking into account the thermal physics, physical and chemical properties of HLMC such as low pressure of saturated vapor of Pb and Pb- Bi in enhanced temperatures, their good heat conductivity and heat capacity, low viscosity, etc.) heat transfer is possible from the molten metal to water and hydrocarbons without heat transferring partitions (that is, by direct contact of the working media). Devices to implement this method of heating liquid and gaseous media provide essential advantages: - A simple design; - None heat-transferring surfaces subject to corrosion, contamination, thermal fatigue, vibration impacts; - A high effectiveness owing to a larger heat exchanging surface per volume unit; - A small hydraulic resistance. The possibility and effectiveness of heating various gaseous and liquid media in their direct contact with molten Pb and Pb-Bi has been substantiated convincingly by experimental results at IPPE. Besides, the following processes of hydrogen-containing media conversion have been proved feasible thereby. 1. Water decomposition into hydrogen and oxygen. The process can develop at temperatures of 400-1000 degree C. It is necessary to provide constant removal of oxygen from the reaction zone and maintain a minimum possible content of chemically active oxygen in the melt. 2. Pyrolytic decomposition of hydrocarbons into carbon and

A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene--toward the formation of methylnaphthalenes.

Science.gov (United States)

Yang, Tao; Muzangwa, Lloyd; Kaiser, Ralf I; Jamal, Adeel; Morokuma, Keiji

2015-09-07

Crossed molecular beam experiments and electronic structure calculations on the reaction of the meta-tolyl radical with vinylacetylene were conducted to probe the formation of methyl-substituted naphthalene isomers. We present the compelling evidence that under single collision conditions 1- and 2-methylnaphthalene can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the meta-tolyl radical and vinylacetylene. The electronic structure calculations, conducted at the UCCSD(T)-F12b/cc-pVDZ//UM06-2x/cc-pVTZ + ZPE(UM06-2x/cc-pVTZ) level of theory, reveal that this reaction is initiated by the barrierless addition of the meta-tolyl radical to the terminal vinyl carbon (C1) of vinylacetylene, via a van-der-Waals complex implying that this mechanism can play a key role in forming methyl-substituted PAHs in low temperature extreme environments such as the low temperature interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer solar system. The reaction mechanism, proposed from the C11H11 potential energy surface, involves a sequence of isomerizations involving hydrogen transfer and ring closure, followed by hydrogen dissociation, which eventually leads to 1- and 2-methylnaphthalene in an overall exoergic process.

Process for in-situ biodegradation of hydrocarbon contaminated soil

International Nuclear Information System (INIS)

Ely, D.L.; Heffner, D.A.

1991-01-01

This patent describes an in situ process for biodegrading hydrocarbons by drawing oxygen into an undisturbed hydrocarbon contaminated zone in a fluid permeable soil. It comprises: establishing a borehole extending from the earth's surface through a hydrocarbon contaminated zone having hydrocarbon degrading microbes therein; lining the borehole with a fluid impermeable liner coaxially spaced and sealingly connected to the inside surface of the borehole and extending from the earth's surface to the hydrocarbon-contaminated zone; the liner including a fluid permeable portion extending from the lower end thereof and through at least a portion of the hydrocarbon contaminated zone, fluidly connecting a source of negative pressure to the fluid impermeable line; evacuating gas from the borehole through the fluid permeable portion of the liner at a rate sufficient to draw air from the earth's surface into the hydrocarbon containing zone; and adjusting the flow rate of the evacuated gas so that the amount of hydrocarbon biodegradation therein is within 50% of the maximum hydrocarbon biodegradation rate as detected by the volume of carbon dioxide in the evacuated gas

Insights into the chemistry of the Claus reaction furnace and waste heat boiler

International Nuclear Information System (INIS)

Clark, P.D.; Dowling, N.I.; Huang, M.

1997-01-01

Methods to deal with the unwanted by-product of acid-gas combustion in the Claus reaction furnace were presented. The by-product, carbon disulfide (CS 2 ), is disturbing because if it is not converted to H 2 S in the first catalytic converter, it will appear as a sulfur emission in the tail gas of plants not using reductive clean-up technology. To address this issue, Claus catalysts have been designed specifically for CS 2 hydrolysis. Studies have been conducted to determine what type of hydrocarbons lead to CS 2 formation. It was concluded that all hydrocarbons result in CS 2 production, but that benzene is particularly difficult. Data for a wide range of acid gas compositions and contaminant hydrocarbons at different process conditions was presented. Methods to destroy CS 2 in the furnace were also identified

Isotopes in oxidation reactions

International Nuclear Information System (INIS)

Stewart, R.

1976-01-01

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

Characterization of low-energy nuclear reactions involving emission of few non-relativistic particles

International Nuclear Information System (INIS)

Martinez Heimann, D.; Pacheco, A.J.; Capurro, O.A.

2010-01-01

We present a general procedure and the associated computational tool for the kinematical description and characterization of nuclear reactions with several fragments in the exit channel. For such processes the emphasis is placed on the purely experimental extraction of the most physically relevant magnitudes and their distributions, which can eventually be compared with the results of generic model calculations. The general capabilities of the approach are illustrated through the results of the application to selected examples, for which various aspects related to inclusive and exclusive measurements are discussed. For the particular case of sequential emission or non-capture breakup we analyze the general problem involved in the determination of intrinsic angular distributions in the rest frame of the decaying nucleus and the design of a specific experiment for a full and uniform coverage of the whole solid angle.

Effects of hydroxylated benzaldehyde derivatives on radiation-induced reactions involving various organic radicals

Science.gov (United States)

Ksendzova, G. A.; Samovich, S. N.; Sorokin, V. L.; Shadyro, O. I.

2018-05-01

In the present paper, the effects of hydroxylated benzaldehyde derivatives and gossypol - the known natural occurring compound - on formation of decomposition products resulting from radiolysis of ethanol and hexane in deaerated and oxygenated solutions were studied. The obtained data enabled the authors to make conclusions about the effects produced by the structure of the compounds under study on their reactivity towards oxygen- and carbon-centered radicals. It has been found that 2,3-dihydroxybenzaldehyde, 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde and 4,6-di-tert-butyl-3-(1,3-dioxane-2-yl)-1,2-dihydroxybenzene are not inferior in efficiency to butylated hydroxytoluene - the industrial antioxidant - as regards suppression of the radiation-induced oxidation processes occurring in hexane. The derivatives of hydroxylated benzaldehydes were shown to have a significant influence on radiation-induced reactions involving α-hydroxyalkyl radicals.

Assessing impediments to hydrocarbon biodegradation in weathered contaminated soils.

Science.gov (United States)

Adetutu, Eric; Weber, John; Aleer, Sam; Dandie, Catherine E; Aburto-Medina, Arturo; Ball, Andrew S; Juhasz, Albert L

2013-10-15

In this study, impediments to hydrocarbon biodegradation in contaminated soils were assessed using chemical and molecular methodologies. Two long-term hydrocarbon contaminated soils were utilised which were similar in physico-chemical properties but differed in the extent of hydrocarbon (C10-C40) contamination (S1: 16.5 g kg(-1); S2: 68.9 g kg(-1)). Under enhanced natural attenuation (ENA) conditions, hydrocarbon biodegradation was observed in S1 microcosms (26.4% reduction in C10-C40 hydrocarbons), however, ENA was unable to stimulate degradation in S2. Although eubacterial communities (PCR-DGGE analysis) were similar for both soils, the alkB bacterial community was less diverse in S2 presumably due to impacts associated with elevated hydrocarbons. When hydrocarbon bioaccessibility was assessed using HP-β-CD extraction, large residual concentrations remained in the soil following the extraction procedure. However, when linear regression models were used to predict the endpoints of hydrocarbon degradation, there was no significant difference (P>0.05) between HP-β-CD predicted and microcosm measured biodegradation endpoints. This data suggested that the lack of hydrocarbon degradation in S2 resulted primarily from limited hydrocarbon bioavailability. Copyright © 2013 Elsevier B.V. All rights reserved.

Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents

Directory of Open Access Journals (Sweden)

Suk-Hwan Kang

2017-10-01

How to Cite: Kang, S.H., Ryu, J.H., Kim, J.H., Kim, H.S., Yang, H.C., Chung, D.Y. (2017. Catalytic Performance for Hydrocarbon Production from Syngas on the Promoted Co-Based Hybrid Catalysts; Influence of Pt Contents. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3: 452-459 (doi:10.9767/bcrec.12.3.592.452-459

Geochemical assessment of light gaseous hydrocarbons in near-surface soils of Kutch-Saurashtra: Implication for hydrocarbon prospects

Science.gov (United States)

Rao, P. Lakshmi Srinivasa; Madhavi, T.; Srinu, D.; Kalpana, M. S.; Patil, D. J.; Dayal, A. M.

2013-02-01

Light hydrocarbons in soil have been used as direct indicators in geochemical hydrocarbon exploration, which remains an unconventional path in the petroleum industry. The occurrence of adsorbed soil gases, methane and heavier homologues were recorded in the near-surface soil samples collected from Kutch-Saurashtra, India. Soil gas alkanes were interpreted to be derived from deep-seated hydrocarbon sources and have migrated to the surface through structural discontinuities. The source of hydrocarbons is assessed to be thermogenic and could have been primarily derived from humic organic matter with partial contribution from sapropelic matter. Gas chromatographic analyses of hydrocarbons desorbed from soil samples through acid extraction technique showed the presence of methane through n-butane and the observed concentrations (in ppb) vary from: methane (C1) from 4-291, ethane (C2) from 0-84, propane (C3) from 0-37, i-butane (iC4) from 0-5 and n-butane (nC4) from 0-4. Carbon isotopes measured for methane and ethane by GC-C-IRMS, range between -42.9‰ to -13.3‰ (Pee Dee Belemnite - PDB) and -21.2‰ to -12.4‰ (PDB), respectively. The increased occurrence of hydrocarbons in the areas near Anjar of Kutch and the area south to Rajkot of Saurashtra signifies the area potential for oil and gas.

Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

Science.gov (United States)

Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

2010-08-03

A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

Constructed wetlands for treatment of dissolved phase hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Moore, B J; Ross, S D [Komex International, Calgary, AB (Canada); Gibson, D [Calgary Univ., AB (Canada); Hardisty, P E [Komex Clarke Bond, Bristol (United Kingdom)

1999-01-01

The use of constructed wetlands as an alternative to conventional treatment of condensate-contaminated groundwater was studied. In 1997 a pilot scale wetland was constructed and implemented at the Gulf Strachan Gas Processing Plant to determine its ability in treating extracted groundwater contaminated with natural gas condensates. This paper presented the results of hydrocarbon removal efficiency, hydrocarbon removal mechanisms, winter operation, and the effect of hydrocarbons on vegetation health. The inflow water to the wetland contains 15 to 20 mg/L of C[sub 5]-C[sub 10] hydrocarbons, including 50 per cent BTEX compounds. During the summer months, hydrocarbon removal efficiency was 100 per cent, but decreased to 60 and 30 per cent in the spring and late fall, respectively. The hydrocarbons not removed in the wetland were eventually removed along the outflow channel. Temperature was determined to be an important factor in the variable removal rates, particularly when there is no aeration. The main hydrocarbon removal mechanisms appear to be volatilization, biodegradation and dilution. At present, plant uptake is not a factor. 12 refs., 1 tab., 3 figs.

Constructed wetlands for treatment of dissolved phase hydrocarbons

International Nuclear Information System (INIS)

Moore, B.J.; Ross, S.D.; Gibson, D.; Hardisty, P.E.

1999-01-01

The use of constructed wetlands as an alternative to conventional treatment of condensate-contaminated groundwater was studied. In 1997 a pilot scale wetland was constructed and implemented at the Gulf Strachan Gas Processing Plant to determine its ability in treating extracted groundwater contaminated with natural gas condensates. This paper presented the results of hydrocarbon removal efficiency, hydrocarbon removal mechanisms, winter operation, and the effect of hydrocarbons on vegetation health. The inflow water to the wetland contains 15 to 20 mg/L of C 5 -C 10 hydrocarbons, including 50 per cent BTEX compounds. During the summer months, hydrocarbon removal efficiency was 100 per cent, but decreased to 60 and 30 per cent in the spring and late fall, respectively. The hydrocarbons not removed in the wetland were eventually removed along the outflow channel. Temperature was determined to be an important factor in the variable removal rates, particularly when there is no aeration. The main hydrocarbon removal mechanisms appear to be volatilization, biodegradation and dilution. At present, plant uptake is not a factor. 12 refs., 1 tab., 3 figs

Quantitative Studies of the Reactions of Hot Tritium Atoms with Hydrocarbons and Hydrocarbon Mixtures; Etudes Quantitatives des Reactions des Atomes Chauds de Tritium avec les Hydrocarbures et les Melanges d'Hydrocarbures; Kolichestvennoe issledovanie reaktsij goryachikh atomov tritiya s gidrouglerodami i smesyami gidrouglerodov; Estudio Cuantitativo de las Reacciones de Atomos de Tritio Calientes con Hidrocarburos y Mezclas de Hidrocarburos

Energy Technology Data Exchange (ETDEWEB)

Urch, D. S.; Welch, M. J. [Department Of Chemistry, Queen Mary College. University of London, London (United Kingdom)

1965-04-15

The kinetic theory of hot-atom reactions is expanded to cover the general system of two reactive species and an inert moderator. From results with a single reactant and moderator, two reactants without moderator, and two reactants with moderator, values of, or ratios of, the reactivity integral I and the average logarithmic energy loss per collision a can be calculated. New results are presented from the reaction of hot tritium produced by the He{sup 3}(n, p)H{sup 3} reaction with the following systems (all contain oxygen scavenger): ethane with helium moderator butane with helium moderator neopentane with helium moderator ethane and butane with and without helium moderator ethane and neopentane with and without helium moderator Values of a and I for the three reactants are calculated from the three types of system and the agreement between the results is discussed in the terms of the accuracy of the model. The results obtained from the different systems agree to within the limits of the experimental error, and this shows that the kinetic theory model can be applied to hot-atom systems with some certainty and that the assumptions made when considering mixtures are reasonable ones. The ratios of the reactivity of the hydrocarbons in mixtures with regard to substitution reactions are not the same as the ratios of the number of hydrogen atoms in the hydrocarbons. The values obtained for these ratios are explained in terms of the values of I and S (the collision cross-section) for the hydrocarbons. (author) [French] Les auteurs etendent la theorie cinetique des reactions des atomes chauds au systeme general forme par deux especes reactives et un ralentisseur inerte. A partir des resultats obtenus au moyen d'un seul corps en reaction et d'un ralentisseur, de deux corps en reaction sans ralentisseur et de deux corps en reaction avec ralentisseur, il est possible de calculer les valeurs ou les rapports de l'integrale de reactivite I, et de la perte d'energie logarithmique

Investigations on the carbon contaminations on the alkali cells of DPAL with hydrocarbon buffer gas

Science.gov (United States)

Li, Zhiyong; Tan, Rongqing; Wang, Yujie; Ye, Qing; Bian, Jintian; Huang, Wei; Li, Hui; Han, Gaoce

2017-10-01

Diode pumped alkali laser (DPAL) with hydrocarbon buffer gases has the features of low threshold and high efficiency. The chemical reaction between alkali and hydrocarbon gases affects the life time of DPAL. In this paper, a method based on Fourier transform infrared spectroscopy and Lambert-Beer law is adopted to find a safe temperature at which DPAL runs for a long term. A theoretical model is established to figure out ways to reduce the peak temperature in the cell window. The results indicates that 170 °C is a safe temperature. Although the absorbance of the cell window to the pump light and alkali laser is lower, there is temperature increase. Small light-transmitting area and air blowing on the windows can reduce the peak temperature effectively. Cooling the cell window is essential and critical in a long-term running DPAL.

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

Directory of Open Access Journals (Sweden)

Suttur Malini

2017-03-01

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

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

Science.gov (United States)

Liechty, Derek S.

2014-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

Reactions of stabilized Criegee Intermediates

Science.gov (United States)

Vereecken, Luc; Harder, Hartwig; Novelli, Anna

2014-05-01

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

Production of hydrocarbons of value

Energy Technology Data Exchange (ETDEWEB)

1931-06-16

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

CO2 as an Oxidant for High Temperature Reactions

Directory of Open Access Journals (Sweden)

Sibudjing eKawi

2015-03-01

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

Direct Reactions

Energy Technology Data Exchange (ETDEWEB)

Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

1963-01-15

In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

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 ...

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

Energy Technology Data Exchange (ETDEWEB)

Rack, E.P.

1980-02-01

The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

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

Energy Technology Data Exchange (ETDEWEB)

Unneberg, E

1997-12-31

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.

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.

A novel phytoremediation technology shown to remediate petroleum hydrocarbons from soils in situ

Energy Technology Data Exchange (ETDEWEB)

Huang, X.D.; Yu, X.M.; Gerhardt, K.; Glick, B.; Greenberg, B [Waterloo Environmental Biotechnology Inc., Hamilton, ON (Canada); Waterloo Univ., ON (Canada). Dept. of Biology

2009-04-01

This article described a newly developed, advanced microbe-enhanced phytoremediation system that can be used to remediate lands polluted by hydrocarbons, salts and metals. The technology uses 3 complementary processes to achieve effective remediation of strongly bound persistent organic pollutants (POPs) from soil. The remediation process involves physical soil treatment, photochemical photooxidation, microbial remediation and growth of plants treated with plant growth promoting rhizobacteria (PGPR). The PGPR-enhanced phytoremediation system (PEPS) alleviates plant stress and increases biodegradation activities, thereby accelerating plant growth in the presence of POPs or poor soils. The PEPS has been used successfully to remove petroleum hydrocarbons (PHCs) from impacted soils in situ at several sites across Canada. Studies have shown that the PHCs are degraded in the rhizosphere. This article also presented a summary of the work conducted at 3 sites in Alberta. It took only 2 years to remediate the 3 sites to levels required for site closure under Alberta Tier 1 guidelines. It was concluded that PEPS is equally effective for total PHC and Fraction 3 CCME hydrocarbons. 1 tab., 3 figs.

Photodynamic activity of polycyclic hydrocarbon

Energy Technology Data Exchange (ETDEWEB)

Epstein, S S

1963-01-01

Exposure of Paramecium caudatum to suspensions of 3,4-benzopyrene, followed by long wave ultraviolet irradiation, results in cell death at times related, inter alia, to carcinogen concentration. Prior to death, the cells exhibit progressive immobilization and blebbing. This photodynamic response is a sensitized photo-oxidation, as it is oxygen-dependent and inhibited by anti-oxidants, such as butylated hydroxy anisole and ..cap alpha..-tocopherol. Protection is also afforded by other agents, including Tweens, tryptophan and certain fractions of plasma proteins. No evidence was found for the involvement of peroxides or sulfhydryl groups. The correlations between photodynamic toxicity and carcinogenicity in a large series of polycyclic hydrocarbons is under investigation. Assays of air extracts for photodynamic toxicity are in progress. Significant toxicity has been found in oxygenated besides aromatic fractions.

Catalytic Upgrading of Biomass-Derived Compounds via C-C Coupling Reactions. Computational and Experimental Studies of Acetaldehyde and Furan Reactions in HZSM-5

Energy Technology Data Exchange (ETDEWEB)

Liu, Cong [Argonne National Lab. (ANL), Argonne, IL (United States); Evans, Tabitha J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Cheng, Lei [Argonne National Lab. (ANL), Argonne, IL (United States); Nimlos, Mark R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Mukarakate, Calvin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Robichaud, David J. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Assary, Rajeev S. [Argonne National Lab. (ANL), Argonne, IL (United States); Curtiss, Larry A. [Argonne National Lab. (ANL), Argonne, IL (United States)

2015-10-02

These catalytic C–C coupling and deoxygenation reactions are essential for upgrading of biomass-derived oxygenates to fuel-range hydrocarbons. Detailed understanding of mechanistic and energetic aspects of these reactions is crucial to enabling and improving the catalytic upgrading of small oxygenates to useful chemicals and fuels. Using periodic density functional theory (DFT) calculations, we have investigated the reactions of furan and acetaldehyde in an HZSM-5 zeolite catalyst, a representative system associated with the catalytic upgrading of pyrolysis vapors. Comprehensive energy profiles were computed for self-reactions (i.e., acetaldehyde coupling and furan coupling) and cross-reactions (i.e., acetaldehyde + furan) of this representative mixture. Major products proposed from the computations are further confirmed using temperature controlled mass spectra measurements. Moreover, the computational results show that furan interacts with acetaldehyde in HZSM-5 via an alkylation mechanism, which is more favorable than the self-reactions, indicating that mixing furans with aldehydes could be a promising approach to maximize effective C–C coupling and dehydration while reducing the catalyst deactivation (e.g., coke formation) from aldehyde condensation.

Development of an Efficient Bacterial Consortium for the Potential Remediation of Hydrocarbons from Contaminated Sites.

Science.gov (United States)

Patowary, Kaustuvmani; Patowary, Rupshikha; Kalita, Mohan C; Deka, Suresh

2016-01-01

The intrinsic biodegradability of hydrocarbons and the distribution of proficient degrading microorganisms in the environment are very crucial for the implementation of bioremediation practices. Among others, one of the most favorable methods that can enhance the effectiveness of bioremediation of hydrocarbon-contaminated environment is the application of biosurfactant producing microbes. In the present study, the biodegradation capacities of native bacterial consortia toward total petroleum hydrocarbons (TPH) with special emphasis to poly aromatic hydrocarbons were determined. The purpose of the study was to isolate TPH degrading bacterial strains from various petroleum contaminated soil of Assam, India and develop a robust bacterial consortium for bioremediation of crude oil of this native land. From a total of 23 bacterial isolates obtained from three different hydrocarbons contaminated samples five isolates, namely KS2, PG1, PG5, R1, and R2 were selected as efficient crude oil degraders with respect to their growth on crude oil enriched samples. Isolates KS2, PG1, and R2 are biosurfactant producers and PG5, R1 are non-producers. Fourteen different consortia were designed involving both biosurfactant producing and non-producing isolates. Consortium 10, which comprises two Bacillus strains namely, Bacillus pumilus KS2 and B. cereus R2 (identified by 16s rRNA sequencing) has shown the best result in the desired degradation of crude oil. The consortium showed degradation up to 84.15% of TPH after 5 weeks of incubation, as revealed from gravimetric analysis. FTIR (Fourier transform infrared) and GCMS (Gas chromatography-mass spectrometer) analyses were correlated with gravimetric data which reveals that the consortium has removed a wide range of petroleum hydrocarbons in comparison with abiotic control including different aliphatic and aromatic hydrocarbons.

The offshore hydrocarbon releases (HCR) database

International Nuclear Information System (INIS)

Bruce, R.A.P.

1995-01-01

Following Cullen Recommendation 39 which states that: ''The regulatory body should be responsible for maintaining a database with regard to hydrocarbon leaks, spills, and ignitions in the Industry and for the benefit of Industry'', HSE Offshore Safety Division (HSE-OSD) has now been operating the Hydrocarbon Releases (HCR) Database for approximately 3 years. This paper deals with the reporting of Offshore Hydrocarbon Releases, the setting up of the HCR Database, the collection of associated equipment population data, and the main features and benefits of the database, including discussion on the latest output information. (author)

Sustainable treatment of hydrocarbon-contaminated industrial land

OpenAIRE

Cunningham, Colin John

2012-01-01

Land contamination by petroleum hydrocarbons is a widespread and global environmental pollution issue from recovery and refining of crude oil and the ubiquitous use of hydrocarbons in industrial processes and applications. Sustainable treatment of hydrocarbon-contaminated industrial land was considered with reference to seven published works on contaminated railway land including the track ballast, crude oil wastes and contaminated refinery soils. A methodology was developed...

Hydrocarbon toxicity: an analysis of AAPCC TESS data.

Science.gov (United States)

Cobaugh, Daniel J; Seger, Donna L; Krenzelok, Edward P

2007-01-01

Human hydrocarbon exposures have the potential to cause significant morbidity and mortality. To determine which hydrocarbons were associated with the most severe adverse outcomes, human exposure data reported to American poison information centers were analyzed. Outcome data for single-substance, hydrocarbon exposures reported to the American Association of Poison Control Centers Toxic Exposure Surveillance System from 1994 through 2003 were analyzed. Only cases with definitive medical outcomes were included. Analyses were stratified by five age groups: 59 years. Hazard factors were determined by calculating the sum of the major effects and fatalities for each hydrocarbon category and dividing this by the total number of exposures for that category. To normalize the data, the overall rate of major effects and deaths for each age group was assigned hazard factor value of 1. Hydrocarbon categories with a HF of > or = 1.5 were included in the final analyses. Estimated rates of major effect and fatal outcomes (outcomes/1000 people) were also calculated. 318,939 exposures were analyzed. Exposures to benzene, toluene/xylene, halogenated hydrocarbons, kerosene and lamp oil resulted in the highest hazard factor values. These data demonstrate that hydrocarbons that are absorbed systemically and those with low viscosities are associated with higher hazard factors. The risks associated with hydrocarbons often implicated in abuse by older children and adolescents are also confirmed.

Thermophilic slurry-phase treatment of petroleum hydrocarbon waste sludges

International Nuclear Information System (INIS)

Castaldi, F.J.; Bombaugh, K.J.; McFarland, B.

1995-01-01

Chemoheterotrophic thermophilic bacteria were used to achieve enhanced hydrocarbon degradation during slurry-phase treatment of oily waste sludges from petroleum refinery operations. Aerobic and anaerobic bacterial cultures were examined under thermophilic conditions to assess the effects of mode of metabolism on the potential for petroleum hydrocarbon degradation. The study determined that both aerobic and anaerobic thermophilic bacteria are capable of growth on petroleum hydrocarbons. Thermophilic methanogenesis is feasible during the degradation of hydrocarbons when a strict anaerobic condition is achieved in a slurry bioreactor. Aerobic thermophilic bacteria achieved the largest apparent reduction in chemical oxygen demand, freon extractable oil, total and volatile solid,s and polycyclic aromatic hydrocarbons (PAHs) when treating oily waste sludges. The observed shift with time in the molecular weight distribution of hydrocarbon material was more pronounced under aerobic metabolic conditions than under strict anaerobic conditions. The changes in the hydrocarbon molecular weight distribution, infrared spectra, and PAH concentrations during slurry-phase treatment indicate that the aerobic thermophilic bioslurry achieved a higher degree of hydrocarbon degradation than the anaerobic thermophilic bioslurry during the same time period

Investigations on potential bacteria for the bioremediation treatment of environments contaminated with hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Lazar, I.; Voicu, A.; Dobrota, S.; Stefanescu, M. [Institute of Biology of Romanian Academy, Bucharest (Romania)] [and others

1995-12-31

In Romania after more than 135 years of oil production and processing, some severe environmental pollution problems have accumulated. In this context a joint research group from Institute of Biology Bucharest and S.C. Petrostar S.A. Ploiesti became involved in a research project on bioremediation of an environment contaminated with hydrocarbon waste. In the first stage of this project, investigations on microbial communities occurring in environments contaminated with oil were carried out. In the second stage, the hundreds of bacterial strains and populations isolated from soils, slops, and water sites contaminated with waste oil and water waste oil mix were submitted to a screening program, to select a naturally occurring mixed culture with a high ability to degrade hydrocarbons.

Degradation of volatile hydrocarbons from steam-classified solid waste by a mixture of aromatic hydrocarbon-degrading bacteria.

Science.gov (United States)

Leahy, Joseph G; Tracy, Karen D; Eley, Michael H

2003-03-01

Steam classification is a process for treatment of solid waste that allows recovery of volatile organic compounds from the waste via steam condensate and off-gases. A mixed culture of aromatic hydrocarbon-degrading bacteria was used to degrade the contaminants in the condensate, which contained approx. 60 hydrocarbons, of which 38 were degraded within 4 d. Many of the hydrocarbons, including styrene, 1,2,4-trimethylbenzene, naphthalene, ethylbenzene, m-/p-xylene, chloroform, 1,3-dichloropropene, were completely or nearly completely degraded within one day, while trichloroethylene and 1,2,3-trichloropropane were degraded more slowly.

Production of hydrocarbons, especially ethylene

Energy Technology Data Exchange (ETDEWEB)

1952-01-17

The invention has for its object a process for the production of gaseous nonsaturated hydrocarbons, particularly ethylene and aromatic hydrocarbons, by starting with hydrocarbon oils entirely of paraffinic nature or their fractions, which consists in putting the separated products in contact with solid inert material especially with porous nonmetallic inert material or of heavy metals or their alloys, maybe in a finely divided state or in the form, of pieces or chips, at a temperature above 500/sup 0/C, or better between 600 and 700/sup 0/C at a velocity per hour of 0.6 to 3.0, and preferably 0.75 to 1.5 parts per volume of products per each part of space volume of catalyst.

Process of distilling heavy hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

1929-12-03

This invention has for its object the distillation of heavy liquid hydrocarbons for the purpose of obtaining lighter hydrocarbons stable and immediately salable for fuels in combustion motors. The process is distinguished by the fact that the heavy hydrocarbon is distilled by means of heating to a temperature in keeping with the nature of the material to be treated up to 350/sup 0/C under pressure or without pressure the distillation being carried out on catalysts containing successively nickel, copper, and iron (3 parts of nickel, 1 part of copper, and 1 part of iron), the vapors produced by this distillation being exposed in turn to the action of catalysts of the same nature and in the same proportion.

Community Structure in Methanogenic Enrichments Provides Insight into Syntrophic Interactions in Hydrocarbon-Impacted Environments

DEFF Research Database (Denmark)

Fowler, Jane; Toth, Courtney R. A.; Gieg, Lisa M.

2016-01-01

, but such information has important implications for bioremediation and microbial enhanced energy recovery technologies. Many factors such as changing environmental conditions or substrate variations can influence the composition and biodegradation capabilities of syntrophic microbial communities in hydrocarbon......The methanogenic biodegradation of crude oil involves the conversion of hydrocarbons to methanogenic substrates by syntrophic bacteria and subsequent methane production by methanogens. Assessing the metabolic roles played by various microbial species in syntrophic communities remains a challenge......-impacted environments. In this study, a methanogenic crude oil-degrading enrichment culture was successively transferred onto the single long chain fatty acids palmitate or stearate followed by their parent alkanes, hexadecane or octadecane, respectively, in order to assess the impact of different substrates...

Seawater-cultured Botryococcus braunii for efficient hydrocarbon extraction.

Directory of Open Access Journals (Sweden)

Kenichi Furuhashi

Full Text Available As a potential source of biofuel, the green colonial microalga Botryococcus braunii produces large amounts of hydrocarbons that are accumulated in the extracellular matrix. Generally, pretreatment such as drying or heating of wet algae is needed for sufficient recoveries of hydrocarbons from B. braunii using organic solvents. In this study, the Showa strain of B. braunii was cultured in media derived from the modified Chu13 medium by supplying artificial seawater, natural seawater, or NaCl. After a certain period of culture in the media with an osmotic pressure corresponding to 1/4-seawater, hydrocarbon recovery rates exceeding 90% were obtained by simply mixing intact wet algae with n-hexane without any pretreatments and the results using the present culture conditions indicate the potential for hydrocarbon milking.Seawater was used for efficient hydrocarbon extraction from Botryococcus braunii. The alga was cultured in media prepared with seawater or NaCl. Hydrocarbon recovery rate exceeding 90% was obtained without any pretreatment.

Influence of growth conditions and surface reaction byproducts on GaN grown via metal organic molecular beam epitaxy: Toward an understanding of surface reaction chemistry

Science.gov (United States)

Pritchett, David; Henderson, Walter; Burnham, Shawn D.; Doolittle, W. Alan

2006-04-01

The surface reaction byproducts during the growth of GaN films via metal organic molecular beam epitaxy (MOMBE) were investigated as a means to optimize material properties. Ethylene and ethane were identified as the dominant surface reaction hydrocarbon byproducts, averaging 27.63% and 7.15% of the total gas content present during growth. Intense ultraviolet (UV) photoexcitation during growth was found to significantly increase the abundance of ethylene and ethane while reducing the presence of H2 and N2. At 920°C, UV excitation was shown to enhance growth rate and crystalline quality while reducing carbon incorporation. Over a limited growth condition range, a 4.5×1019-3.4×1020 cm-3 variation in carbon incorporation was achieved at constant high vacuum. Coupled with growth rate gains, UV excitation yielded films with ˜58% less integrated carbon content. Structural material property variations are reported for various ammonia flows and growth temperatures. The results suggest that high carbon incorporation can be achieved and regulated during MOMBE growth and that in-situ optimization through hydrocarbon analysis may provide further enhancement in the allowable carbon concentration range.

Molecular characterization of autochthonous hydrocarbon utilizing ...

African Journals Online (AJOL)

Prof. Ogunji

Materials and Methods ... culturable hydrocarbon utilizing bacteria (HUB) were enumerated by vapour phase ... hydrocarbon utilizing bacterial isolates by boiling method according to ... obtained in this investigation are consistent with past field studies (Kostka et ... Microbial and other related changes in a Niger sediment.

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-04-01

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

Mineral oil hydrocarbons in food - a review.

Science.gov (United States)

Grob, Koni

2018-06-12

Work on mineral oil hydrocarbons (MOH) contaminating food is reviewed up to about 2010, when the subject received broad publicity. It covers the period of the main discoveries and elimination or reduction of the dominant sources: release agents used in industrial bakeries, spraying of rice, additions to animal feed, contamination of edible oils from various sources and migration from paperboard packaging. In most cases highly refined ("white") oils were involved, but also technical oils, e.g. from the environment, and more or less crude oil fractions from jute and sisal bags. There were numerous unexpected sources, and there might still be more of those. The exposure of the consumers to MOH must have been markedly reduced in the meantime. Environmental influx may have become dominant, particularly when taking into account that these MOH go through several degradation processes which might enrich the species resisting metabolic elimination. Major gaps are in the systematic investigation of sources and the largely unavoidable levels from environmental contamination, but also in the toxicological evaluation of the various types of hydrocarbons. A regulation is overdue that avoids the present discrepancy between the low tolerance to MOH perceived as contaminants and the very high legal limits for some applications - the MOH are largely the same.

Volatilisation of aromatic hydrocarbons from soil

DEFF Research Database (Denmark)

Lindhardt, B.; Christensen, T.H.

1996-01-01

The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic...... aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 mu g/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under...... saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch - by a factor of 8 to 25 - than expected for natural organic matter. The fluxes were also estimated using an analytical...

Oils; lubricants; paraffin-wax compositions; hydrocarbon condensation products

Energy Technology Data Exchange (ETDEWEB)

1934-04-04

Petroleum hydrocarbons such as gasoline, kerosene, Diesel fuel oil, lubricating-oil, and paraffin wax, and like hydrocarbons such as are obtainable from shale oil and by the hydrogenation of carbonaceous materials, are improved by addition of products obtained by condensing a cyclic hydrocarbon with a saturated dihalogen derivative of an aliphatic hydrocarbon containing less than five carbon atoms. The addition of the condensation products increases the viscosity of the hydrocarbon oils specified, and is particularly useful in the case of lubricating-oils; addition of the condensation products to paraffin wax increases the transparency and adherent properties of the wax, and is useful in the manufacture of moulded articles such as candles; the products may also be used in solid lubricating-compositions.

Total petroleum hydrocarbons in sediments from the coastline and mangroves of the northern Persian Gulf.

Science.gov (United States)

Mohebbi-Nozar, Seyedeh Laili; Zakaria, Mohamad Pauzi; Ismail, Wan Ruslan; Mortazawi, Mohammad Seddiq; Salimizadeh, Maryam; Momeni, Mohammad; Akbarzadeh, Gholamali

2015-06-15

To provide baseline information for the marine ecosystem of Hormozgan province, the distribution of petroleum hydrocarbons was evaluated in 52 stations involved in the mangrove and coastline ecosystem. Coastline sampling sites included areas facing harbor, river, domestic and industrial discharge. Sediment samples were analyzed based on ultraviolet fluorescence spectroscopy. Petroleum hydrocarbons showed narrow variations ranging from non-detectable (ND) to 1.71 and from 0.2 to 0.63μg/g dry weight for coastline and mangrove sediments, respectively. The detected concentrations for total petroleum hydrocarbons were lower than guideline values for ecological risk. Furthermore, the minimum environmental risk was confirmed by background levels for the Persian Gulf, the Sea of Oman, and detected values for reference areas. The results were regarded as background data in the studied area, and, considering the rapid expansion of activities related to the petroleum industry in Hormozgan province, the continuous monitoring of pollutants is recommended. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; Lucia M. Petkovic

2004-11-01

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

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

Science.gov (United States)

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

2018-01-01

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

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

Science.gov (United States)

Liechty, Derek S.

2013-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

A method of refining aromatic hydrocarbons from coal chemical production

Energy Technology Data Exchange (ETDEWEB)

Zieborak, K.; Koprowski, A.; Ratajczak, W.

1979-10-01

A method is disclosed for refining aromatic hydrocarbons of coal chemical production by contact of liquid aromatic hydrocarbons and their mixtures with a strongly acid macroporous sulfocationite in the H-form at atmospheric pressure and high temperature. The method is distinguished in that the aromatic hydrocarbons and their mixtures, from which alkali compounds have already been removed, are supplied for refinement with the sulfocationite with simultaneous addition of olefin derivatives of aromatic hydrocarbons, followed by separation of pure hydrocarbons by rectification. Styrene or alpha-methylstyrene is used as the olefin derivatives of the aromatic hydrocarbons. The method is performed in several stages with addition of olefin derivatives of aromatic hydrocarbons at each stage.

Process for recovery of liquid hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Millar, J.F.; Cockshott, J.E.

1978-04-11

Methane is recovered as a gas for discharge to a pipeline from a gas stream containing methane and heavier hydrocarbons, principally ethane and propane. Separation is accomplished by condensing the heavier hydrocarbons and distilling the methane therefrom. A liquid product (LPG) comprising the heavier hydrocarbons is subsequently recovered and transferred to storage. Prior to being discharged to a pipeline, the recovered methane gas is compressed and in undergoing compression the gas is heated. The heat content of the gas is employed to reboil the refrigerant in an absorption refrigeration unit. The refrigeration unit is used to cool the LPG prior to its storage.

Worldwide overview of hydrocarbons and perspectives

International Nuclear Information System (INIS)

Tonnac, Alain de; Perves, Jean-Pierre

2013-12-01

This publication presents and comments data regarding the share of hydrocarbons in the world energy consumption, hydrocarbon trade flows, the new situation created by the emergence of shale hydrocarbons and the consequences for the world economy, and possible risks. The authors first comment the evolution of energy consumption and outline that the objectives of CO 2 and greenhouse gas emission will not be reached (these emissions increased in 2012 and in 2013). They indicate the emission situation in the USA and Japan, and notice that the objectives defined by the IEA are quite different from those defined by the EU. They analyse the evolutions by distinguishing different periods: 2005-2008 as a reference period, 2008-2012 as a period of change, and the current period as a period of flow inversion. Then, the authors propose two different scenarios of evolution of economic and energy policies. The evolution of hydrocarbon demand is commented, and the levels of reserves (oil, conventional gas, coal, nuclear fuels) are discussed. The market evolution is also discussed, not only from an economic point of view, but also in relationship with geopolitics. The authors notably outline that the energy price is different from one country to the other, discuss the issue of hydrocarbon refining, the role of CO 2 tax

Hydrocarbon-degradation by Isolate Pseudomonas lundensis UTAR FPE2

Directory of Open Access Journals (Sweden)

Adeline, S. Y. Ting

2009-01-01

Full Text Available In this study, the potential of isolate Pseudomonas lundensis UTAR FPE2 as a hydrocarbon degrader was established. Their biodegradation activity was first detected with the formation of clearing zones on Bushnell-Hass agar plates, with the largest diameter observed on plates supplemented with paraffin, followed by mineral oil and petrol. Utilization of hydrocarbon sources were again detected in broth cultures supplemented with similar hydrocarbon substrates, where the mean viable cell count recovered from hydrocarbon-supplemented broth cultures were higher than the initial inoculum except for napthalene. In both tests, the isolate showed higher degradability towards aliphatic hydrocarbon sources, and the least activity towards the aromatic hydrocarbon naphthalene. The isolate P. lundensis UTAR FPE2 (8 log10 cfu/mL also degraded crude diesel sample, with 69% degradation during the first three days. To conclude, this study suggests the potential use of this isolate for bioremediation of hydrocarbon-contaminated environments.

Selective detection of isomers with photoionization mass spectrometry for studies of hydrocarbon flame chemistry

International Nuclear Information System (INIS)

Cool, Terrill A.; Nakajima, Koichi; Mostefaoui, Toufik A.; Qi, Fei; McIlroy, Andrew; Westmoreland, Phillip R.; Law, Matthew E.; Poisson, Lionel; Peterka, Darcy S.; Ahmed, Musahid

2003-01-01

We report the first use of synchrotron radiation, continuously tunable from 8 to 15 eV, for flame-sampling photoionization mass spectrometry (PIMS). Synchrotron radiation offers important advantages over the use of pulsed vacuum ultraviolet lasers for PIMS; these include superior signal-to-noise, soft ionization, and access to photon energies outside the limited tuning ranges of current VUV laser sources. Near-threshold photoionization efficiency measurements were used to determine the absolute concentrations of the allene and propyne isomers of C 3 H 4 in low-pressure laminar ethylene-oxygen and benzene-oxygen flames. Similar measurements of the isomeric composition of C 2 H 4 O species in a fuel-rich ethylene-oxygen flame revealed the presence of substantial concentrations of ethenol (vinyl alcohol) and acetaldehyde. Ethenol has not been previously detected in hydrocarbon flames. Absolute photoionization cross sections were measured for ethylene, allene, propyne, and acetaldehyde, using propene as a calibration standard. PIE curves are presented for several additional reaction intermediates prominent in hydrocarbon flames

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.

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

Science.gov (United States)

Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;

High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

Energy Technology Data Exchange (ETDEWEB)

Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

2007-01-01

Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10^-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C₆H₁₁) and π-allyl C₆H₉, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C₆H₉, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C₆H₉ was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E_2u mode of free benzene, which leads to catalysis. Linear C₆ (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

Maillard Reaction: review

Directory of Open Access Journals (Sweden)

Júlia d'Almeida Francisquini

2017-11-01

Full Text Available Maillard reaction is an important subject of study in food science and technology and different areas of knowledge are involved such as chemistry, food engineering, nutrition and food technology. The objective of this paper is to present the basic concepts of the Maillard reaction, such as the reaction stages, the main compounds producced and some technological consequences for dairy products.

Structure, function and carcinogenicity of metabolites of methylated and non-methylated polycyclic aromatic hydrocarbons: a comprehensive review.

Science.gov (United States)

Flesher, James W; Lehner, Andreas F

2016-01-01

The Unified Theory of PAH Carcinogenicity accommodates the activities of methylated and non-methylated polycyclic aromatic hydrocarbons (PAHs) and states that substitution of methyl groups on meso-methyl substituted PAHs with hydroxy, acetoxy, chloride, bromide or sulfuric acid ester groups imparts potent cancer producing properties. It incorporates specific predictions from past researchers on the mechanism of carcinogenesis by methyl-substituted hydrocarbons, including (1) requirement for metabolism to an ArCH2X type structure where X is a good leaving group and (2) biological substitution of a meso-methyl group at the most reactive center in non-methylated hydrocarbons. The Theory incorporates strong inferences of Fieser: (1) The mechanism of carcinogenesis involves a specific metabolic substitution of a hydrocarbon at its most reactive center and (2) Metabolic elimination of a carcinogen is a detoxifying process competitive with that of carcinogenesis and occurring by a different mechanism. According to this outlook, chemical or biochemical substitution of a methyl group at the reactive meso-position of non-methylated hydrocarbons is the first step in the mechanism of carcinogenesis for most, if not all, PAHs and the most potent metabolites of PAHs are to be found among the meso methyl-substituted hydrocarbons. Some PAHs and their known or potential metabolites and closely related compounds have been tested in rats for production of sarcomas at the site of subcutaneous injection and the results strongly support the specific predictions of the Unified Theory.

Potential hydrocarbon producing species of Western Ghats, Tamil Nadu, India

Energy Technology Data Exchange (ETDEWEB)

Augustus, G.D.P.S.; Jayabalan, M.; Rajarathinam, K. [Research Centre in Bombay, V.H.N.S.N. College, Virudhunagar (India); Ray, A.K. [Sardar Patel Univ., Anand (India). Dept. of Chemistry; Seiler, G.J. [USDA, ARS, Northern Crop Science Lab., Fargo, ND (United States)

2002-09-01

The decline in the world supplies of hydrocarbons has led to the search for alternate sources of fuel and chemicals. Plant species are potential sources of hydrocarbons. Large-scale screening of plants growing in the Western Ghats, Tamil Nadu, India was conducted to assess the hydrocarbon production and the type of isoprene compound(s) present. Three species contained more than 3% hydrocarbon. Sarcostemma brevistigma had the highest concentration of hydrocarbon with 3.6%. Seven species contained more than 2% of hydrocarbons among the plant species screened. The hydrocarbon fraction of Ficus elastica (leaf) had a gross heat value of 9834 cal/g (41.17 MJ/kg), which is close to the caloric value of fuel oil. Six hydrocarbon fractions contained gross heat values of more than 9000 cal/g (37.68 MJ/kg). Of the 13 species hydrocarbon fraction analysed, seven species contained cis-polyisoprene compounds, while two species contained trans-polyisoprenes. Cis and trans polyisoprenes are potential alternative energy sources for fuel and/or as industrial raw materials. (author)

AD1995: NW Europe's hydrocarbon industry

International Nuclear Information System (INIS)

Glennie, K.; Hurst, A.

1996-01-01

This volume concerns itself with wide-ranging aspects of the upstream hydro-carbon industry over the whole of NW Europe. As such, the book contrasts with many thematic volumes by presenting a broad range of topics side-by-side. One section of the book looks back at the history of geological exploration and production, and provides an overview of hydrocarbon exploration across NW Europe. Another section covers the state of the art in hydrocarbon exploration and production. This includes an update on computer-based basin modelling overpressure systems, innovations in reservoir engineering and reserve estimation, 3D seismic and the geochemical aspects of secondary migration. The final section of the book takes a look into the future. This covers the remaining hydrocarbon resources of the North Sea, managing risk in oil field development, oil field economics, and pollution and the environment. It is the editors' hope that several key areas of NW Europe's upstream oil industry have been usefully summarized in the volume. (Author)

Enrichment of light hydrocarbon mixture

Science.gov (United States)

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

2010-08-10

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.

Halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1975--February 14, 1976

International Nuclear Information System (INIS)

Rack, E.P.

1976-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, are being studied in gaseous, high pressure, and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and other organic systems. Experimental and theoretical data are presented in the following areas: systematics of iodine hot atom reactions in halomethanes, reactions and systematics of iodine reactions with pentene and butene isomers, radiative neutron capture activated reactions of iodine with acetylene, gas to liquid to solid transition in hot atom chemistry, kinetic theory applications of hot atom reactions and the mathematical development of caging reactions, solvent dependence of the stereochemistry of the 38 Cl for Cl substitution following 37 Cl(n,γ) 38 Cl in liquid meso and dl-(CHFCl) 2 . A technique was also developed for the radioassay of Al in urine specimens

Purifying hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Dunstan, A E

1918-06-03

Ligroin, kerosene, and other distillates from petroleum and shale oil, are purified by treatment with a solution of a hypochlorite containing an excess of alkali. The hydrocarbon may be poured into brine, the mixture stirred, and an electric current passed through. Heat may be applied.

Improvements in the biotreatment of soil contaminated by heavy hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Paquin, J. [Sanexen Environmental Services Inc., Varennes, PQ (Canada)

2006-07-01

This presentation discussed improvements in the biotreatment of soil contaminated by heavy hydrocarbons. The presentation provided information on the background for the investigation such as: difficulty for biotreatment in soil to deal with heavy weathered hydrocarbons and fine grained soils; the involvement of the Montreal Centre of Excellence for Brownfield Remediation (MCEBR) to develop state of the art environmental solutions; and, the selection of Sanexen as the organization with the best price and best performance warranty to perform the required decontamination. The objectives of the study were to improve the performance of biotreatment of soil contaminated with heavy petroleum hydrocarbons; reduce soil biotreatment costs by 30 per cent; improve knowledge and understanding for this type of treatment; and, better identify constraints and optimal strategies in view of these constraints. Specific objectives that were discussed included: improving the microbial flora, attaining a favorable soil temperature at a low cost, identifying the best amendments for bulking of soil, increasing bio-availability of the contaminants, and identifying optimal mechanical handling of the soil. The presentation discussed soils treated; research and development carried out; standard method of biotreatment; alternative methods tested; initial investigation by the MCEBR; pilot test carried out by Sanexen; and, results of the pilot test. As part of the research program with MCEBR, soils that received different amendments were tested at the Biotechnology Research Institute (BRI) of the National Research Council for their ability to degrade added hexadecane and naphthalene. Soil at various stages of the treatment was also sampled and tested by the (BRI). It was concluded that the biotreatment of heavy hydrocarbons in fine grained soils is feasible and that the techniques used reduced biotreatment costs by approximately 25 per cent.

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

Science.gov (United States)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

Toxicity of jet fuel aliphatic and aromatic hydrocarbon mixtures on human epidermal Keratinocytes: evaluation based on in vitro cytotoxicity and interleukin-8 release

Energy Technology Data Exchange (ETDEWEB)

Yang, Jen-Hung (Chung-Shan Medical University Hospital, Department of Dermatology, Taichung, Taiwan, R.O.C); Lee, Chia-Hue; Tsang, Chau-Loong [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); Monteiro-Riviere, Nancy A.; Riviere, Jim E. [North Carolina State University, Center for Chemical Toxicology Research and Pharmacokinetics (CCTRP), Raleigh, NC (United States); Chou, Chi-Chung [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan)

2006-08-15

Jet fuels are complex mixtures of aliphatic (ALI) and aromatic (ARO) hydrocarbons that vary significantly in individual cytotoxicity and proinflammatory activity in human epidermal keratinocytes (HEK). In order to delineate the toxicological interactions among individual hydrocarbons in a mixture and their contributions to cutaneous toxicity, nine ALI and five ARO hydrocarbons were each divided into five (high/medium/low cytotoxic and strong/weak IL-8 induction) groups and intra/inter-mixed to assess for their mixture effects on HEK mortality and IL-8 release. Addition of single hydrocarbon to JP-8 fuel was also evaluated for their changes in fuel dermatotoxicity. The results indicated that when hydrocarbons were mixed, HEK mortality and IL-8 release were not all predictable by their individual ability affecting these two parameters. The lowest HEK mortality (7%) and the highest IL-8 production were induced with mixtures including high cytotoxic and weak IL-8 inductive ARO hydrocarbons. Antagonistic reactions not consistently correlated with ALI carbon chain length and ARO structure were evident and carried different weight in the overall mixture toxicities. Single addition of benzene, toluene, xylene or ethylbenzene for up to tenfold in JP-8 did not increase HEK mortality while single addition of ALI hydrocarbons exhibited dose-related differential response in IL-8. In an all ALI environment, no single hydrocarbon is the dominating factor in the determination of HEK cytotoxicity while deletion of hexadecane resulted in a 2.5-fold increase in IL-8 production. Overall, decane, undecane and dodecane were the major hydrocarbons associated with high cytotoxicity while tetradecane, pentadecane and hexadecane were those which had the greatest buffering effect attenuating dermatotoxicity. The mixture effects must be considered when evaluating jet fuel toxicity to HEK. (orig.)

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-03-18

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

Culture-dependent characterization of hydrocarbon utilizing bacteria ...

African Journals Online (AJOL)

EARNEST

Hydrocarbons interact with the environment and micro- organisms determining the .... it is pertinent to study the community dynamics of hydrocarbon degrading bacteria ... Chikere CB (2013). Application of molecular microbiology techniques in.

Identifying future directions for subsurface hydrocarbon migration research

Science.gov (United States)

Leifer, I.; Clark, J. F.; Luyendyk, B.; Valentine, D.

Subsurface hydrocarbon migration is important for understanding the input and impacts of natural hydrocarbon seepage on the environment. Great uncertainties remain in most aspects of hydrocarbon migration, including some basic mechanisms of this four-phase flow of tar, oil, water, and gas through the complex fracture-network geometry particularly since the phases span a wide range of properties. Academic, government, and industry representatives recently attended a workshop to identify the areas of greatest need for future research in shallow hydrocarbon migration.Novel approaches such as studying temporal and spatial seepage variations and analogous geofluid systems (e.g., geysers and trickle beds) allow deductions of subsurface processes and structures that remain largely unclear. Unique complexities exist in hydrocarbon migration due to its multiphase flow and complex geometry, including in-situ biological weathering. Furthermore, many aspects of the role of hydrocarbons (positive and negative) in the environment are poorly understood, including how they enter the food chain (respiration, consumption, etc.) and “percolate” to higher trophic levels. But understanding these ecological impacts requires knowledge of the emissions' temporal and spatial variability and trajectories.

33 CFR 157.166 - Hydrocarbon emissions.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Hydrocarbon emissions. 157.166 Section 157.166 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED... Crude Oil Washing (COW) System on Tank Vessels Cow Operations § 157.166 Hydrocarbon emissions. If the...

Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species during Methanol to Olefins Conversion over H-SSZ-13

NARCIS (Netherlands)

Borodina, E.; Meirer, F.; Lezcano-Gonzalez, I.; Mokhtar, M.; Asiri, A. M.; Al-Thabaiti, S. A.; Basahel, S. N.; Ruiz-Martinez, J.; Weckhuysen, B. M.

The formation of hydrocarbon species during the methanol to olefins (MTO) reaction over zeolite H-SSZ-13 has been systematically studied at reaction temperatures between 573 and 723 K with a combination of operando UV-vis spectroscopy and online gas chromatography. It was found that the applied

Soil sealing degree as factor influencing urban soil contamination with polycyclic aromatic hydrocarbons (PAHs

Directory of Open Access Journals (Sweden)

Mendyk Łukasz

2016-03-01

Full Text Available The objective of the study was to determine role of soil sealing degree as the factor influencing soil contamination with polycyclic aromatic hydrocarbons (PAHs. The study area included four sampling sites located within the administrative boundaries of the Toruń city, Poland. Sampling procedure involved preparing soil pits representing three examples of soil sealing at each site: non-sealed soil as a control one (I and two degrees of soil sealing: semi-pervious surface (II and totally impervious surface (III. Together with basic properties defined with standard procedures (particle size distribution, pH, LOI, content of carbonates content of selected PAHs was determined by dichloromethane extraction using gas chromatography with mass spectrometric detection (GC-MS. Obtained results show that urban soils in the city of Toruń are contaminated with polycyclic aromatic hydrocarbons. Soil sealing degree has a strong influence on the soil contamination with polycyclic aromatic hydrocarbons. Totally sealed soils are better preserved from atmospheric pollution including PAHs. Combustion of grass/wood/coal was the main source of determined PAHs content in examined soils.

Distribution and geochemical application of aromatic hydrocarbons in crude oils

International Nuclear Information System (INIS)

Asif, M.; Tahira, F.

2007-01-01

Distribution of aromatic hydrocarbons was studied in a set of crude oils, five from northern Indus basin of potwar area and two from southern Indus basin. Diaromatic and triaromatic hydrocarbons were separated from highly complex mixture of sedimentary organic matter by using liquid chromatography techniques such as column chromatography, TLC and GC-FID. These classes of compounds were identified to alkylated isomers of naphthalenes and phenanthrenes by using reference chromatograms and literature data. High concentration of di-,tri- and tetra-methyl naphthalenes was observed in all crude oils except Kal. The relative increase in concentration of alkyl naphthalenes was found as moved to higher methyl substituted isomers. This suggests that they are the product of sedimentary alkylation reactions during catagensis and metagensis. The significant concentration of methyl phenanthrenes indicated source of organic matter. High levels of both 1-MP and 9-MP showed marine and terrestrial source of organic matter except Umer crude oil which is most likely to have terrestrial origin. The ratios of beta-substituted to the alpha-substituted isomers of both alkyl naphthalenes and alkyl phenanthrene were used to assess the thermal maturity of sedimentary organic matter, which revealed high maturity level of Dhurnal, Pindori, Badin and Toot crude oils. (author)

Investigating bioremediation of petroleum hydrocarbons through landfarming using apparent electrical conductivity measurements

Science.gov (United States)

Van De Vijver, Ellen; Van Meirvenne, Marc; Seuntjens, Piet

2015-04-01

Bioremediation of soil contaminated with petroleum hydrocarbons through landfarming has been widely applied commercially at large scale. Biodegradation is one of the dominant pollutant removal mechanisms involved in landfarming, but strongly depends on the environmental conditions (e.g. presence of oxygen, moisture content). Conventionally the biodegradation process is monitored by the installation of field monitoring equipment and repeated sample collection and analysis. Because the presence of petroleum hydrocarbons and their degradation products can affect the electrical properties of the soil, proximal soil sensors such as electromagnetic induction (EMI) sensors may provide an alternative to investigate the biodegradation process of these contaminants. We investigated the relation between the EMI-based apparent electrical conductivity (ECa) of a landfarm soil and the presence and degradation status of petroleum hydrocarbons. The 3 ha study area was located in an oil refinery complex contaminated with petroleum hydrocarbons, mainly composed of diesel. At the site, a landfarm was constructed in 1999. The most recent survey of the petroleum hydrocarbon concentrations was conducted between 2011 and 2013. The sampling locations were defined by a grid with a 10 m by 10 m cell size and on each location a sample was taken from four successive soil layers with a thickness of 0.5 m each. Because the survey was carried out in phases using different georeferencing methods, the final dataset suffered from uncertainty in the coordinates of the sampling locations. In September 2013 the landfarm was surveyed for ECa with a multi-receiver electromagnetic induction sensor (DUALEM-21S) using motorized conveyance. The horizontal measurement resolution was 1 m by 0.25 m. On each measurement location the sensor recorded four ECa values representative of measurement depths of 0.5 m, 1.0 m, 1.6 m and 3.2 m. After the basic processing, the ECa measurements were filtered to remove

Performance estimation of ejector cycles using heavier hydrocarbon refrigerants

International Nuclear Information System (INIS)

Kasperski, Jacek; Gil, Bartosz

2014-01-01

Computer software basing on theoretical model of Huang et al. with thermodynamic properties of hydrocarbons was prepared. Investigation was focused on nine hydrocarbons: propane, butane, iso-butane, pentane, iso-pentane, hexane, heptane and octane. A series of calculations was carried out for the generator temperature between 70 and 200 °C, with assumed temperatures of evaporation 10 °C and condensation 40 °C. Calculation results show that none of the hydrocarbons enables high efficiency of a cycle in a wide range of temperature. Each hydrocarbon has its own maximal entrainment ratio at its individual temperature of optimum. Temperatures of entrainment ratios optimum increase according to the hydrocarbon heaviness with simultaneous increase of entrainment ratio peak values. Peak values of the COP do not increase according to the hydrocarbons heaviness. The highest COP = 0.32 is achieved for iso-butane at 102 °C and the COP = 0.28 for pentane at 165 °C. Heptane and octane can be ignored. - Highlights: • Advantages of use of higher hydrocarbons as ejector refrigerants were presumed. • Computer software basing on theoretical model of Huang et al. (1999) was prepared. • Optimal temperature range of vapor generation for each hydrocarbon was calculated

Chemical transport reactions

CERN Document Server

Schäfer, Harald

2013-01-01

Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

Polycyclic’ Aromatic Hydrocarbon Induced Intracellular Signaling and Lymphocyte Apoptosis

DEFF Research Database (Denmark)

Schneider, Alexander M.

The aryl hydrocarbon (dioxin) receptor (AhR) is a transcription factor possessing high affinity to potent environmental pollutants, polycyclic aromatic hydrocarbons (PAH) and related halogenated hydrocarbons (e.g. dioxins). Numerous research attribute toxicity of these compounds to the receptor...

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

International Nuclear Information System (INIS)

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

2009-01-01

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

[Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation].

Science.gov (United States)

Sirota, T V

2015-01-01

An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

Optimising the bio-piling of weathered hydrocarbons within a risk management framework

International Nuclear Information System (INIS)

Hough, R.; Brassington, K.; Sinke, A.; Crossley, J.; Paton, G.; Semple, K.; Risdon, G.; Jacobson, Ch.; Daly, P.; Jackman, S.; Lethbridge, G.; Pollard, S.

2005-01-01

Thirty years of research into petroleum microbiology and bio-remediation have bypassed an important observation - that many hydrocarbon contaminated sites posing potential risks to human health harbour weathered, 'mid-distillate' or heavy oils rather than 'fresh product'. Ex-situ bio-piling is an important technology for treating soils contaminated with weathered hydrocarbons. However, its performance continues to be represented by reference to reductions in the hydrocarbon 'load' in the soils being treated, rather than reductions in the risks posed by the hydrocarbon contamination. The absence of 'risk' from the vocabulary of many operators and remediation projects reduces stakeholder (regulatory, investor, landowner, and public) confidence in remediation technologies, and subsequently limits the market potential of these technologies. Stakeholder confidence in the bio-piling of weathered hydrocarbons may be improved by demonstrating process optimisation within a validated risk management framework. To address these issues, a consortium led by Cranfield University's Integrated Waste Management Centre has secured funding from the UK Government's Bio-remediation LINK programme. Project PROMISE (involving BP, SecondSite Regeneration Ltd., Dew Remediation Ltd., TES Bretby (Mowlem Group), technology translators PERA, and academics from Aberdeen, Cranfield and Lancaster Universities) aims to improve market confidence in bio-piling by demonstrating how this treatment may be applied within a risk management context. For weathered hydrocarbons in particular, the underpinning scientific components of process control, waste diagnostics, environmental fate modelling, and risk assessment have yet to be fully integrated to allow bio-piling projects to be verified with improved confidence. The Joint Research Council Review of Bio-remediation recognised this in calling explicitly for the positioning of bio-remediation within a risk management framework. The PERF report (Thermo

Method for production of unsaturated gaseous hydrocarbons, particularly ethylene, and of aromatic hydrocarbons, adapted as motor fuels

Energy Technology Data Exchange (ETDEWEB)

1952-10-24

A method is described for the production of unsaturated gaseous hydrocarbons, in particular of ethylene, and of aromatic hydrocarbons from hydrocarbon oils or from fractions of the same, characterized by the fact that the raw materials are brought into contact with porous, inert substances in the form of fine distribution or of pieces at a temperature of above 500 and in particular from 600 to about 700/sup 0/C and with a traversing speed of from 0.3 up to about 3.0 volumetric parts, preferably up to 1.5 volumetric parts of raw material per volumetric part of the chamber and per hour.

Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

NARCIS (Netherlands)

Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

2009-01-01

Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions

Contribution to the study of catalytic hydrogen-deuterium exchange between hydrogen and hydrocarbons

International Nuclear Information System (INIS)

Ravoire, J.

1958-01-01

The hydrogen-deuterium exchange between molecular hydrogen and hydrocarbons over a platinum and charcoal catalyst was studied in a static system. The change in isotopic composition of molecular hydrogen was followed by a thermal conductivity method. Cyclo-pentane and cyclohexane were chosen because of their stability. A reversible inactivation of the catalyst was observed with both hydrocarbons. The reasons for this inactivation are unknown but it was shown that reactivation led to satisfactory reproducibility. A kinetic study was done with cyclohexane in the range 30 to 160 deg. C, and 40 to 360 mm for the pressure of hydrogen, and 10 to 70 mm for the pressure of cyclohexane. The order of the reaction with respect to cyclohexane pressure is always close to zero; the order with respect to that of hydrogen is 0.5 above 100 deg. C. It decreases with increasing temperature and becomes negative (-0.5 at 30 deg. C), characterizing an inhibition by hydrogen. At the same time, the apparent activation energy goes from 6 to 13 kcal/mole. (author) [fr

Effects of environmental pollution with aromatic hydrocarbons on endocrine and metabolic functions of the human placenta.

Science.gov (United States)

Wierzba, Waldemar; Radowicki, Stanisław; Bojar, Iwona; Pinkas, Jarosław

2018-03-14

Phenol and 1-hydroxypyrene are biological markers of exposure to polycyclic aromatic hydrocarbons (PAH) that have certain negative effects on parenchymal organs such as the human placenta. The literature presents only few reports regarding the effects of elevated PAH levels on the functions of the human placenta. The aim of the work is to assess the effects of elevated PAH levels in excreted urine on the endocrine and metabolic functions of the human placenta obtained from a normal pregnancy. Tissue material from 50 afterbirths from Płock constituted a study group, whereas 50 afterbirths from Kutno constituted a control group. Immunohistochemical reactions with the peroxidase method using LSAB kits (DAKO, Denmark) were performed. The extent and intensity of reactions were analysed. The levels of phenols and 1-hydroxypyrene in the excreted urine of pregnant women (undergoing delivery) were detected using gas chromatography and colorimetry. The statistical analysis used the PQStat v.1.6.2 software; moreover, t-student and chi-square tests were used. Differences were considered to be significant at the significance level of 95% (p<0.05). The levels of phenol and 1-hydroxypyrene in the excreted urine were demonstrated to be statistically significantly higher in patients living in the area of Płock. Statistically lower expression of placental glutathione transferase and lower immunohistochemical demonstration of the placental phosphatase activity were observed in placentas from Płock. It has been demonstrated that the expression of the oestrogen receptor activity and placental gonadotropin is significantly higher in placentas from areas not contaminated with aromatic hydrocarbons (Kutno). The course of pregnancy in the environment with elevated levels of aromatic hydrocarbons leads to impaired placental functioning and reduced endocrine and metabolic activity of the placenta.

Reactions of ruthenium and osmium cluster carbonyls with heteroatom-substituted and functionalized alkynes

International Nuclear Information System (INIS)

Koridze, A.A.

2000-01-01

The results of studies of the reactions of ruthenium and osmium cluster carbonyls with metal (M = Re, Mn, Fe) alkynes, silylalkynes, propargyl alcohols and their derivatives, diynes, enynes, and ferrocenylacetylene are summarized. Intramolecular rearrangements in the cluster complexes including migrations of carbonyl, hydride, and hydrocarbon ligands and the metal core reorganization are considered [ru

Constitutive Expression of Aryl Hydrocarbon Receptor in Keratinocytes Causes Inflammatory Skin Lesions

OpenAIRE

Tauchi, Masafumi; Hida, Azumi; Negishi, Takaaki; Katsuoka, Fumiki; Noda, Shuhei; Mimura, Junsei; Hosoya, Tomonori; Yanaka, Akinori; Aburatani, Hiroyuki; Fujii-Kuriyama, Yoshiaki; Motohashi, Hozumi; Yamamoto, Masayuki

2005-01-01

Occupational and environmental exposure to polycyclic aromatic hydrocarbons (PAHs) has been suggested to provoke inflammatory and/or allergic disorders, including asthma, rhinitis, and dermatitis. The molecular mechanisms of this PAH-mediated inflammation remain to be clarified. Previous studies implied the involvement of PAHs as irritants and allergens, with the reactive oxygen species generated from the oxygenated PAHs believed to be an exacerbating factor. It is also possible that PAHs con...

Analysis of coupled mass transfer and sol-gel reaction in a two-phase system

NARCIS (Netherlands)

Castelijns, H.J.; Huinink, H.P.; Pel, L.; Zitha, P.L.J.

2006-01-01

The coupled mass transfer and chemical reactions of a gel-forming compound in a two-phase system were studied in detail. Tetra-methyl-ortho-silicate (TMOS) is often used as a precursor in sol-gel chemistry to produce silica gels in aqueous systems. TMOS can also be mixed with many hydrocarbons

Methods for reformation of gaseous hydrocarbons using electrical discharge

KAUST Repository

Cha, Min Suk

2017-02-16

Methods for the reformation of gaseous hydrocarbons are provided. The methods can include forming a bubble containing the gaseous hydrocarbon in a liquid. The bubble can be generated to pass in a gap between a pair of electrodes, whereby an electrical discharge is generated in the bubble at the gap between the electrodes. The electrodes can be a metal or metal alloy with a high melting point so they can sustain high voltages of up to about 200 kilovolts. The gaseous hydrocarbon can be combined with an additive gas such as molecular oxygen or carbon dioxide. The reformation of the gaseous hydrocarbon can produce mixtures containing one or more of H2, CO, H2O, CO2, and a lower hydrocarbon such as ethane or ethylene. The reformation of the gaseous hydrocarbon can produce low amounts of CO2 and H2O, e.g. about 15 mol-% or less.

Methods for reformation of gaseous hydrocarbons using electrical discharge

KAUST Repository

Cha, Min; Zhang, Xuming

2017-01-01

Methods for the reformation of gaseous hydrocarbons are provided. The methods can include forming a bubble containing the gaseous hydrocarbon in a liquid. The bubble can be generated to pass in a gap between a pair of electrodes, whereby an electrical discharge is generated in the bubble at the gap between the electrodes. The electrodes can be a metal or metal alloy with a high melting point so they can sustain high voltages of up to about 200 kilovolts. The gaseous hydrocarbon can be combined with an additive gas such as molecular oxygen or carbon dioxide. The reformation of the gaseous hydrocarbon can produce mixtures containing one or more of H2, CO, H2O, CO2, and a lower hydrocarbon such as ethane or ethylene. The reformation of the gaseous hydrocarbon can produce low amounts of CO2 and H2O, e.g. about 15 mol-% or less.

Bioremediation of Petroleum Hydrocarbon Contaminated Sites

Energy Technology Data Exchange (ETDEWEB)

Fallgren, Paul

2009-03-30

Bioremediation has been widely applied in the restoration of petroleum hydrocarbon-contaminated. Parameters that may affect the rate and efficiency of biodegradation include temperature, moisture, salinity, nutrient availability, microbial species, and type and concentration of contaminants. Other factors can also affect the success of the bioremediation treatment of contaminants, such as climatic conditions, soil type, soil permeability, contaminant distribution and concentration, and drainage. Western Research Institute in conjunction with TechLink Environmental, Inc. and the U.S. Department of Energy conducted laboratory studies to evaluate major parameters that contribute to the bioremediation of petroleum-contaminated drill cuttings using land farming and to develop a biotreatment cell to expedite biodegradation of hydrocarbons. Physical characteristics such as soil texture, hydraulic conductivity, and water retention were determined for the petroleum hydrocarbon contaminated soil. Soil texture was determined to be loamy sand to sand, and high hydraulic conductivity and low water retention was observed. Temperature appeared to have the greatest influence on biodegradation rates where high temperatures (>50 C) favored biodegradation. High nitrogen content in the form of ammonium enhanced biodegradation as well did the presence of water near field water holding capacity. Urea was not a good source of nitrogen and has detrimental effects for bioremediation for this site soil. Artificial sea water had little effect on biodegradation rates, but biodegradation rates decreased after increasing the concentrations of salts. Biotreatment cell (biocell) tests demonstrated hydrocarbon biodegradation can be enhanced substantially when utilizing a leachate recirculation design where a 72% reduction of hydrocarbon concentration was observed with a 72-h period at a treatment temperature of 50 C. Overall, this study demonstrates the investigation of the effects of

Formation of microspheres under the action of femtosecond laser radiation on titanium samples in hydrocarbons

Science.gov (United States)

Kochuev, D. A.; Khorkov, K. S.; Ivashchenko, A. V.; Prokoshev, V. G.; Arakelian, S. M.

2018-01-01

This work describes the original method of laser synthesis of microspheres which contain titanium carbide. The formation of microspheres is carried out by the action of femtosecond laser radiation on the surface of titanium in the reaction medium - the ultimate hydrocarbon. The resulting microspheres have a high surface smoothness, a narrow particle size distribution, an average size of 1-3 μm. They can be used in applications of additive engineering, powder metallurgy as the main raw material, or as an alloying additive.

Cobalt catalysts for the conversion of methanol and for Fischer-tropsch synthesis to produce hydrocarbons

International Nuclear Information System (INIS)

Mauldin, C.H.; Davis, S.M.; Arcuri, K.B.

1987-01-01

A regeneration stable catalyst is described for the conversion at reaction conditions of methanol or synthesis gas to liquid hydrocarbons which consists essentially of from about 2 percent to about 25 percent cobalt, based on the weight of the catalyst composition, composited with titania, or a titania-containing support, to which is added sufficient of a zirconium, hafnium, cerium, or uranium promoter to provide a weight ratio of the zirconium, hafnium, cerium, or uranium metal:cobalt greater than about 0.101:1

Degradation of petroleum hydrocarbons in a laboratory aquifer column

International Nuclear Information System (INIS)

Billowits, M.; Whyte, L.; Greer, C.; Ramsay, J.

1998-01-01

One of the primary mechanisms for eliminating hydrocarbon pollutants from the environment is degradation of hydrocarbons by indigenous microorganisms. This report describes a study in which samples from a petroleum polluted shallow aquifer in the Yukon were used which contained a hundred times greater concentration of psychrotropic bacteria than mesophilic bacteria. Results showed a maximum degradation of 47 per cent of the total petroleum hydrocarbon in columns which simulated the aquifer conditions and to which nutrients were added. It was concluded that although in this case bioaugmentation of the columns with a psychrotropic hydrocarbon-degrading consortium increased microbial numbers, total petroleum hydrocarbon degradation was not much greater than could be achieved by remediation with nutrients alone

Hydrocarbons in Argentina: networks, territories, integration

International Nuclear Information System (INIS)

Carrizo, S.C.

2003-12-01

Argentinean hydrocarbons networks have lived a huge reorganizing the structure, after the State reform in the 90's. Activities deregulation and the privatization of YPF and Gas del Estado forced the sector re-concentration, since then dominated by foreign companies, leaded by Repsol YPF. The hydrocarbons federalization contributed to the weakening and un-capitalization loss of wealth of the State. These changes resulted in an increase of the hydrocarbons production allowing to achieve the self-supply. Nevertheless, the expansion of internal networks has not been large enough to ensure the coverage of new requirements. Besides, several infrastructures have been built up to join external markets. National networks are connected to those of near neighboring countries. This integration is an opportunity for the 'South Cone' countries to enhance their potentials. In the country, hydrocarbons territories undergo the reorganizing the structure effects (unemployment, loss of territorial identity, etc). With many difficulties and very different possibilities, those territories, like Comodoro Rivadavia, Ensenada et and Bahia Blanca, look for their re-invention. (author)

Role of soot in the transport of chlorine in hydrocarbon-air diffusion flames

International Nuclear Information System (INIS)

Venkatesh, S.; Saito, K.; Stencel, J.M.; Majidi, V.; Owens, M.

1991-01-01

Soot is an inevitable product of incomplete combustion in many practical combustion systems such as automobiles, incinerators and furnaces. Recent studies on chlorinated hydrocarbon combustion have shown that soot and other praticulates (eg. fly ash) play an important role in secondary reactions leading to the formation of chlorine substituted polyaromatic hydrocarbons (PAHs). In order to attain very high destruction efficiencies the fundamental chemical and physical processes that are associated with combustion, and post-combustion cleanup must be well understood. In order to understand the effect of chlorine on the soot formed in a combustion system, fundamental studies using a coflow laminar hydrocarbon-air diffusion flame have been carried out. Phenomenological studies have revealed the effect of chlorine on the visible structure of the flame. Soot inception activation energies were estimated for methane, ethane and ethylene diffusion flames for the case of with and without chlorine addition. No significant difference in the activation energy was estimated for either case. The effect of chlorine on the soot escape rate of an acetylene diffusion flame was estimated. The soot formed in these diffusion flames was analyzed for chlorine using scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) and by laser induced plasma spectroscopy (LIPS). REsults from these techniques indicate the presence of chlorine in the soot formed. In this paper a chemical scheme to explain the chlorine found in the soot is proposed based on known theories of soot formation

Bioremediation in soil contaminated with hydrocarbons in Colombia.

OpenAIRE

María Alejandra Trujillo Toro; Juan Fernando Ramírez Quirama

2012-01-01

This study analyzes bioremediation processes of hydrocarbon contaminated soils in Colombia as a sustainable alternative to the deterioration of environmental quality by hydrocarbon spillage. According to national and international environmental law, all waste contaminated with hydrocarbons is considered dangerous waste, and therefore it cannot be released in the ground, water or be incinerated. Such legislation has motivated companies around the world to implement treatment processes for cont...

Hydrocarbon productivities in different Botryococcus strains: comparative methods in product quantification.

Science.gov (United States)

Eroglu, Ela; Okada, Shigeru; Melis, Anastasios

2011-08-01

Six different strains of the green microalgae Botryococcus belonging to the A-race or B-race, accumulating alkadiene or botryococcene hydrocarbons, respectively, were compared for biomass and hydrocarbon productivities. Biomass productivity was assessed gravimetrically upon strain growth in the laboratory under defined conditions. Hydrocarbon productivities were measured by three different and independent experimental approaches, including density equilibrium of the intact cells and micro-colonies, spectrophotometric analysis of hydrocarbon extracts, and gravimetric quantitation of eluted hydrocarbons. All three hydrocarbon-quantitation methods yielded similar results for each of the strains examined. The B-race microalgae Botryococcus braunii var. Showa and Kawaguchi-1 constitutively accumulated botryococcene hydrocarbons equivalent to 30% and 20%, respectively, of their overall biomass. The A-race microalgae Botryococcus braunii, varieties Yamanaka, UTEX 2441 and UTEX LB572 constitutively accumulated alkadiene hydrocarbons ranging from 14% to 13% and 10% of their overall biomass, respectively. Botryococcus sudeticus (UTEX 2629), a morphologically different green microalga, had the lowest hydrocarbon accumulation, equal to about 3% of its overall biomass. Results validate the density equilibrium and spectrophotometric analysis methods in the quantitation of botryococcene-type hydrocarbons. These analytical advances will serve in the screening and selection of B. braunii and of other microalgae in efforts to identify those having a high hydrocarbon content for use in commercial applications.

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

Directory of Open Access Journals (Sweden)

Tomescu Cristian

2017-01-01

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