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Sample records for catalytic cycle direct

  1. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  2. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

    The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.

  3. Direct catalytic hydrothermal liquefaction of spirulina to biofuels with hydrogen

    Science.gov (United States)

    Zeng, Qin; Liao, Hansheng; Zhou, Shiqin; Li, Qiuping; Wang, Lu; Yu, Zhihao; Jing, Li

    2018-01-01

    We report herein on acquiring biofuels from direct catalytic hydrothermal liquefaction of spirulina. The component of bio-oil from direct catalytic hydrothermal liquefaction was similar to that from two independent processes (including liquefaction and upgrading of biocrude). However, one step process has higher carbon recovery, due to the less loss of carbons. It was demonstrated that the yield and HHV of bio-oil from direct catalytic algae with hydrothermal condition is higher than that from two independent processes.

  4. Direct catalytic olefination of alcohols with sulfones.

    Science.gov (United States)

    Srimani, Dipankar; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

    2014-10-06

    The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Computational Modeling of the Catalytic Cycle of Glutathione Peroxidase Nanomimic.

    Science.gov (United States)

    Kheirabadi, Ramesh; Izadyar, Mohammad

    2016-12-29

    To elucidate the role of a derivative of ebselen as a mimic of the antioxidant selenoenzyme glutathione peroxidase, density functional theory and solvent-assisted proton exchange (SAPE) were applied to model the reaction mechanism in a catalytic cycle. This mimic plays the role of glutathione peroxidase through a four-step catalytic cycle. The first step is described as the oxidation of 1 in the presence of hydrogen peroxide, while selenoxide is reduced by methanthiol at the second step. In the third step of the reaction, the reduction of selenenylsulfide occurs by methanthiol, and the selenenic acid is dehydrated at the final step. Based on the kinetic parameters, step 4 is the rate-determining step (RDS) of the reaction. The bond strength of the atoms involved in the RDS is discussed with the quantum theory of atoms in molecules (QTAIM). Low value of electron density, ρ(r), and positive Laplacian values are the evidence for the covalent nature of the hydrogen bonds rupture (O 30 -H 31 , O 33 -H 34 ). A change in the sign of the Laplacian, L(r), from the positive value in the reactant to a negative character at the transition state indicates the depletion of the charge density, confirming the N 5 -H 10 and O 11 -Se 1 bond breaking. The analysis of electron location function (ELF) and localized orbital locator (LOL) of the Se 1 -N 5 and Se 1 -O 11 bonds have been done by multi-WFN program. High values of ELF and LOL at the transition state regions between the Se, N, and O atoms display the bond formation. Finally, the main donor-acceptor interaction energies were analyzed using the natural bond orbital analysis for investigation of their stabilization effects on the critical bonds at the RDS.

  6. Directional synthesis of ethylbenzene through catalytic transformation of lignin.

    Science.gov (United States)

    Fan, Minghui; Jiang, Peiwen; Bi, Peiyan; Deng, Shumei; Yan, Lifeng; Zhai, Qi; Wang, Tiejun; Li, Quanxin

    2013-09-01

    Transformation of lignin to ethylbenzene can provide an important bulk raw material for the petrochemical industry. This work explored the production of ethylbenzene from lignin through the directional catalytic depolymerization of lignin into the aromatic monomers followed by the selective alkylation of the aromatic monomers. For the first step, the aromatics selectivity of benzene derived from the catalytic depolymerization of lignin reached about 90.2 C-mol% over the composite catalyst of Re-Y/HZSM-5 (25). For the alkylation of the aromatic monomers in the second step, the highest selectivity of ethylbenzene was about 72.3 C-mol% over the HZSM-5 (25) catalyst. The reaction pathway for the transformation of lignin to ethylbenzene was also addressed. Present transformation potentially provides a useful approach for the production of the basic petrochemical material and development of high-end chemicals utilizing lignin as the abundant natural aromatic resource. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Direct instrumental identification of catalytically active surface sites

    Science.gov (United States)

    Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

    2017-09-01

    The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

  8. Catalytic silica particles via template-directed molecular imprinting

    Energy Technology Data Exchange (ETDEWEB)

    Markowitz, M.A.; Kust, P.R.; Deng, G.; Schoen, P.E.; Dordick, J.S.; Clark, D.S.; Gaber, B.P.

    2000-02-22

    The surfaces of silica particle were molecularly imprinted with an {alpha}-chymotrypsin transition-state analogue (TSA) by utilizing the technique of template-directed synthesis of mineralized materials. The resulting catalytic particles hydrolyzed amides in an enantioselective manner. A mixture of a nonionic surfactant and the acylated chymotrysin TSA, with the TSA acting as the headgroup at the surfactant-water interface, was used to form a microemulsion for silica particle formation. Incorporation of amine-, dihydroimidazole-, and carboxylate-terminated trialkoxysilanes into the particles during imprinting resulted in enhancement of the rates of amide hydrolysis. Acylated imprint molecules formed more effective imprints in the presence of the functionalized silanes than nonacylated imprint molecules. Particles surface-imprinted with the chymotrypsin TSA were selective for the trypsin substrate, and particles surface-imprinted with the L-isomer of the enzyme TSA were enantioselective for the D-isomer of the substrate.

  9. Forced thermal cycling of catalytic reactions: experiments and modelling

    DEFF Research Database (Denmark)

    Jensen, Søren; Olsen, Jakob Lind; Thorsteinsson, Sune

    2007-01-01

    Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed...... at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained...

  10. Catalysis by Glomerella cingulata cutinase requires conformational cycling between the active and inactive states of its catalytic triad.

    Science.gov (United States)

    Nyon, Mun Peak; Rice, David W; Berrisford, John M; Hounslow, Andrea M; Moir, Arthur J G; Huang, Huazhang; Nathan, Sheila; Mahadi, Nor Muhammad; Bakar, Farah Diba Abu; Craven, C Jeremy

    2009-01-09

    Cutinase belongs to a group of enzymes that catalyze the hydrolysis of esters and triglycerides. Structural studies on the enzyme from Fusarium solani have revealed the presence of a classic catalytic triad that has been implicated in the enzyme's mechanism. We have solved the crystal structure of Glomerella cingulata cutinase in the absence and in the presence of the inhibitors E600 (diethyl p-nitrophenyl phosphate) and PETFP (3-phenethylthio-1,1,1-trifluoropropan-2-one) to resolutions between 2.6 and 1.9 A. Analysis of these structures reveals that the catalytic triad (Ser136, Asp191, and His204) adopts an unusual configuration with the putative essential histidine His204 swung out of the active site into a position where it is unable to participate in catalysis, with the imidazole ring 11 A away from its expected position. Solution-state NMR experiments are consistent with the disrupted configuration of the triad observed crystallographically. H204N, a site-directed mutant, was shown to be catalytically inactive, confirming the importance of this residue in the enzyme mechanism. These findings suggest that, during its catalytic cycle, cutinase undergoes a significant conformational rearrangement converting the loop bearing the histidine from an inactive conformation, in which the histidine of the triad is solvent exposed, to an active conformation, in which the triad assumes a classic configuration.

  11. Effects of catalytic hydrotreating on light cycle oil fuel quality

    International Nuclear Information System (INIS)

    Anabtawi, J.A.; Ali, S.A.

    1991-01-01

    This paper reports on a pilot plant study that was conducted to evaluate three commercial catalysts for hydrotreating of light cycle oil to reduce its aromatic content and improve the cetane index. The operating parameters were varied between 325 and 400 degrees C, 1 and 3 h - 1 , and 4 and 10 MPa at 535 L/L. The data showed that, in general, the product density and aromatic content decreased as the temperature or pressure increased or space velocity decreased. The cetane index improvement ranged from 7.3 to 10.0 for the Ni-W/Al 2 O 3 catalyst and from 6.1 to 10.1 for the Ni-Mo/Al 2 O 3 catalysts. The catalyst performance was evaluated in terms of hydrodesulfurization, hydrodenitrogenation, hydrogenation, aromatic saturation, and hydrogen consumption. This study confirms that light cycle oil can be hydrotreated to improve its cetane quality, thus increasing the extent of its blending ratio into the diesel pool

  12. Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

    Science.gov (United States)

    Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

    2016-04-04

    Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98% isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Direct catalytic cross-coupling of organolithium compounds

    NARCIS (Netherlands)

    Giannerini, Massimo; Fananas Mastral, Martin; Feringa, Ben L.

    Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern

  14. Probing the electrostatics of active site microenvironments along the catalytic cycle for Escherichia coli dihydrofolate reductase.

    Science.gov (United States)

    Liu, C Tony; Layfield, Joshua P; Stewart, Robert J; French, Jarrod B; Hanoian, Philip; Asbury, John B; Hammes-Schiffer, Sharon; Benkovic, Stephen J

    2014-07-23

    Electrostatic interactions play an important role in enzyme catalysis by guiding ligand binding and facilitating chemical reactions. These electrostatic interactions are modulated by conformational changes occurring over the catalytic cycle. Herein, the changes in active site electrostatic microenvironments are examined for all enzyme complexes along the catalytic cycle of Escherichia coli dihydrofolate reductase (ecDHFR) by incorporation of thiocyanate probes at two site-specific locations in the active site. The electrostatics and degree of hydration of the microenvironments surrounding the probes are investigated with spectroscopic techniques and mixed quantum mechanical/molecular mechanical (QM/MM) calculations. Changes in the electrostatic microenvironments along the catalytic environment lead to different nitrile (CN) vibrational stretching frequencies and (13)C NMR chemical shifts. These environmental changes arise from protein conformational rearrangements during catalysis. The QM/MM calculations reproduce the experimentally measured vibrational frequency shifts of the thiocyanate probes across the catalyzed hydride transfer step, which spans the closed and occluded conformations of the enzyme. Analysis of the molecular dynamics trajectories provides insight into the conformational changes occurring between these two states and the resulting changes in classical electrostatics and specific hydrogen-bonding interactions. The electric fields along the CN axes of the probes are decomposed into contributions from specific residues, ligands, and solvent molecules that make up the microenvironments around the probes. Moreover, calculation of the electric field along the hydride donor-acceptor axis, along with decomposition of this field into specific contributions, indicates that the cofactor and substrate, as well as the enzyme, impose a substantial electric field that facilitates hydride transfer. Overall, experimental and theoretical data provide evidence for

  15. The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

    Science.gov (United States)

    Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

    2017-12-01

    The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Direct cycle type nuclear power plant

    International Nuclear Information System (INIS)

    Tagawa, Hisato; Ibe, Hidefumi.

    1990-01-01

    In a direct cycle type nuclear power plant such as BWR type reactor, since oxygen atoms in reactor water are actuvated by neutron irradiation in the reactor core, carry over of the thus formed radioactive nitrogen atoms causes increase in the dosage in a turbine system. Since 16 N accompanies in the main steams in the chemical form of 16 NO, it can not effectively be removed in a nitrogen removing device. In view of the above, hydrogen atom concentration is reduced by adding metals having high reaction with hydrogen atoms, for example, silver ions, chromium ions, or ruthenium ions are added to reactor water. Then, equilibrium concentration of 16 NO in water is reduced by suppressing the reaction: 16 NO 2 + H → 16 NO + OH. (T.M.)

  17. Thickness-controlled direct growth of nanographene and nanographite film on non-catalytic substrates

    Science.gov (United States)

    Du, Lei; Yang, Liu; Hu, Zhiting; Zhang, Jiazhen; Huang, Chunlai; Sun, Liaoxin; Wang, Lin; Wei, Dacheng; Chen, Gang; Lu, Wei

    2018-05-01

    Metal-catalyzed chemical vapor deposition (CVD) has been broadly employed for large-scale production of high-quality graphene. However, a following transfer process to targeted substrates is needed, which is incompatible with current silicon technology. We here report a new CVD approach to form nanographene and nanographite films with accurate thickness control directly on non-catalytic substrates such as silicon dioxide and quartz at 800 °C. The growth time is as short as a few seconds. The approach includes using 9-bis(diethylamino)silylanthracene as the carbon source and an atomic layer deposition (ALD) controlling system. The structure of the formed nanographene and nanographite films were characterized using atomic force microscopy, high resolution transmission electron microscopy, Raman scattering, and x-ray photoemission spectroscopy. The nanographite film exhibits a transmittance higher than 80% at 550 nm and a sheet electrical resistance of 2000 ohms per square at room temperature. A negative temperature-dependence of the resistance of the nanographite film is also observed. Moreover, the thickness of the films can be precisely controlled via the deposition cycles using an ALD system, which promotes great application potential for optoelectronic and thermoelectronic-devices.

  18. Catalytic Cycle of Haloalkane Dehalogenases Toward Unnatural Substrates Explored by Computational Modeling.

    Science.gov (United States)

    Marques, Sérgio M; Dunajova, Zuzana; Prokop, Zbynek; Chaloupkova, Radka; Brezovsky, Jan; Damborsky, Jiri

    2017-08-28

    The anthropogenic toxic compound 1,2,3-trichloropropane is poorly degradable by natural enzymes. We have previously constructed the haloalkane dehalogenase DhaA31 by focused directed evolution ( Pavlova, M. et al. Nat. Chem. Biol. 2009 , 5 , 727 - 733 ), which is 32 times more active than the wild-type enzyme and is currently the most active variant known against that substrate. Recent evidence has shown that the structural basis responsible for the higher activity of DhaA31 was poorly understood. Here we have undertaken a comprehensive computational study of the main steps involved in the biocatalytic hydrolysis of 1,2,3-trichloropropane to decipher the structural basis for such enhancements. Using molecular dynamics and quantum mechanics approaches we have surveyed (i) the substrate binding, (ii) the formation of the reactive complex, (iii) the chemical step, and (iv) the release of the products. We showed that the binding of the substrate and its transport through the molecular tunnel to the active site is a relatively fast process. The cleavage of the carbon-halogen bond was previously identified as the rate-limiting step in the wild-type. Here we demonstrate that this step was enhanced in DhaA31 due to a significantly higher number of reactive configurations of the substrate and a decrease of the energy barrier to the S N 2 reaction. C176Y and V245F were identified as the key mutations responsible for most of those improvements. The release of the alcohol product was found to be the rate-limiting step in DhaA31 primarily due to the C176Y mutation. Mutational dissection of DhaA31 and kinetic analysis of the intermediate mutants confirmed the theoretical observations. Overall, our comprehensive computational approach has unveiled mechanistic details of the catalytic cycle which will enable a balanced design of more efficient enzymes. This approach is applicable to deepen the biochemical knowledge of a large number of other systems and may contribute to robust

  19. Direct catalytic production of sorbitol from waste cellulosic materials.

    Science.gov (United States)

    Ribeiro, Lucília Sousa; Órfão, José J de Melo; Pereira, Manuel Fernando Ribeiro

    2017-05-01

    Cotton wool, cotton textile, tissue paper and printing paper, all potential waste cellulosic materials, were directly converted to sorbitol using a Ru/CNT catalyst in the presence of H 2 and using only water as solvent, without any acids. Conversions up to 38% were attained for the raw substrates, with sorbitol yields below 10%. Ball-milling of the materials disrupted their crystallinity, allowing reaching 100% conversion of cotton wool, cotton textile and tissue paper after 4h, with sorbitol yields around 50%. Mix-milling these materials with the catalyst greatly enhanced their conversion rate, and the materials were efficiently converted to sorbitol with a yield around 50% in 2h. However, ball- and mix-milled printing paper presented a conversion of only 50% after 5h, with sorbitol yields of 7%. Amounts of sorbitol of 0.525, 0.511 and 0.559g could be obtained from 1g of cotton wool, cotton textile and tissue paper, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Direct Hysteresis Heating of Catalytically Active Ni–Co Nanoparticles as Steam Reforming Catalyst

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Engbæk, Jakob Soland; Vendelbo, Søren Bastholm

    2017-01-01

    We demonstrated a proof-of-concept catalytic steam reforming flow reactor system heated only by supported magnetic nickel–cobalt nanoparticles in an oscillating magnetic field. The heat transfer was facilitated by the hysteresis heating in the nickel–cobalt nanoparticles alone. This produced...... a sufficient power input to equilibrate the reaction at above 780 °C with more than 98% conversion of methane. The high conversion of methane indicated that Co-rich nanoparticles with a high Curie temperature provide sufficient heat to enable the endothermic reaction, with the catalytic activity facilitated...... by the Ni content in the nanoparticles. The magnetic hysteresis losses obtained from temperature-dependent hysteresis measurements were found to correlate well with the heat generation in the system. The direct heating of the catalytic system provides a fast heat transfer and thereby overcomes the heat...

  1. Life Cycle Assessment Applied to Naphtha Catalytic Reforming Analyse de cycle de vie appliquée au reformage catalytique du naphta

    OpenAIRE

    Portha J.-F.; Jaubert J.-N.; Louret S.; Pons M.-N.

    2010-01-01

    Facing the increase of environmental concerns in the oil and gas industry, engineers and scientists need information to assess sustainability of chemical processes. Among the different methods available, Life Cycle Assessment (LCA) is widely used. In this study, LCA is applied to a catalytic reforming process using the Eco- Indicator 99 as life cycle impact assessment method. The main identified environmental impacts are fossil fuels consumption, climate change and respiratory effects du...

  2. Accumulating the hydride state in the catalytic cycle of [FeFe]-hydrogenases

    Science.gov (United States)

    Winkler, Martin; Senger, Moritz; Duan, Jifu; Esselborn, Julian; Wittkamp, Florian; Hofmann, Eckhard; Apfel, Ulf-Peter; Stripp, Sven Timo; Happe, Thomas

    2017-07-01

    H2 turnover at the [FeFe]-hydrogenase cofactor (H-cluster) is assumed to follow a reversible heterolytic mechanism, first yielding a proton and a hydrido-species which again is double-oxidized to release another proton. Three of the four presumed catalytic intermediates (Hox, Hred/Hred and Hsred) were characterized, using various spectroscopic techniques. However, in catalytically active enzyme, the state containing the hydrido-species, which is eponymous for the proposed heterolytic mechanism, has yet only been speculated about. We use different strategies to trap and spectroscopically characterize this transient hydride state (Hhyd) for three wild-type [FeFe]-hydrogenases. Applying a novel set-up for real-time attenuated total-reflection Fourier-transform infrared spectroscopy, we monitor compositional changes in the state-specific infrared signatures of [FeFe]-hydrogenases, varying buffer pH and gas composition. We selectively enrich the equilibrium concentration of Hhyd, applying Le Chatelier's principle by simultaneously increasing substrate and product concentrations (H2/H+). Site-directed manipulation, targeting either the proton-transfer pathway or the adt ligand, significantly enhances Hhyd accumulation independent of pH.

  3. Gate-to-Gate Life Cycle Assessment for Determining Carbon Footprint of Catalytic Converter Assembly Process

    Directory of Open Access Journals (Sweden)

    A. N. Mustfizul Karim

    2017-03-01

    Full Text Available With the pursuit of embracing the circular economy, having upward trend in vehicle sales and environmental concern, sustainability has become an imperative part of the global automotive manufacturing strategies. One of the tactics to achieve this sustainable goal is to conserve and enhance the resource base by salvaging the embedded values from end-of-life product and for which, the remanufacturing can be considered as one of the most prominent epitome. Even though many of the auto parts like engine, transmissions, starters, alternators and etc. have been assessed for remanufacturability since last few decades, being a major component of a car body the Catalytic Converter (CC still remains unfocused in literature. However, to examine the remanufacturability of CC, a comprehensive study for assessing its economic, social, and environmental impact is inevitable. Therefore, with an underlying aim of designing the remanufacturable CC, in this endeavour an attempt has made to evaluate the environmental impact of its welding operations by means of energy consumption through gate-to-gate life cycle assessment. Real life data are collected from a Local Malaysian CC manufacturer. The obtained results show that the welding section has a carbon footprint of 0.203 kgCO2e/unit with major emission coming from the plasma arc welding. In addition to that, it is also observed that the value of carbon footprint is not only sensitive to the emission factor and processing time, but also it is responsive to the nature of the processing operations. Certainly, this observation will motivate to change the product design from the prospect of remanufacturing.

  4. Theoretical Investigation of the Enzymatic Phosphoryl Transfer of β-phosphoglucomutase: Revisiting Both Steps of the Catalytic Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Elsasser, Brigitta M.; Dohmeier-Fischer, Silvia; Fels, Gregor

    2012-07-12

    Enzyme catalyzed phosphate transfer is a part of almost all metabolic processes. Such reactions are of central importance for the energy balance in all organisms and play important roles in cellular control at all levels. Mutases transfer a phosphoryl group while nucleases cleave the phosphodiester linkages between two nucleotides. The subject of our present study is the Lactococcus lactis β-phosphoglucomutase (β-PGM), which effectively catalyzes the interconversion of β-D-glucose-1-phosphate (β-G1P) to β- D-glucose-6-phosphate (β-G6P) and vice versa via stabile intermediate β-D-glucose-1,6-(bis)phosphate (β-G1,6diP) in the presence of Mg2+. In this paper we revisited the reaction mechanism of the phosphoryl transfer starting from the bisphosphate β-G1,6diP in both directions (toward β-G1P and β-G6P) combining docking techniques and QM/MM theoretical method at the DFT/PBE0 level of theory. In addition we performed NEB (nudged elastic band) and free energy calculations to optimize the path and to identify the transition states and the energies involved in the catalytic cycle. Our calculations reveal that both steps proceed via dissociative pentacoordinated phosphorane, which is not a stabile intermediate but rather a transition state. In addition to the Mg2+ ion, Ser114 and Lys145 also play important roles in stabilizing the large negative charge on the phosphate through strong coordination with the phosphate oxygens and guiding the phosphate group throughout the catalytic process. The calculated energy barrier of the reaction for the β-G1P to β-G1,6diP step is only slightly higher than for the β-G1,6diP to β-G6P step (16.10 kcal mol-1 versus 15.10 kcal mol-1) and is in excellent agreement with experimental findings (14.65 kcal mol-1).

  5. Catalytic performance and durability of Ni/AC for HI decomposition in sulfur–iodine thermochemical cycle for hydrogen production

    International Nuclear Information System (INIS)

    Fu, Guangshi; He, Yong; Zhang, Yanwei; Zhu, Yanqun; Wang, Zhihua; Cen, Kefa

    2016-01-01

    Highlights: • The relation between Ni content and Ni particle dispersion were disclosed. • The effect of Ni content on the catalytic activity of Ni/AC catalyst was revealed. • The optimal content of Ni for Ni/AC catalysts in HI decomposition was found. - Abstract: This work reports the Ni content effect on the Ni/AC catalytic performance in the HI decomposition reaction of the sulfur–iodine (SI) thermochemical cycle for hydrogen production and the Ni/AC catalyst durability in a long-term test. Accordingly, five catalysts with the Ni content ranging from 5% to 15% were prepared by an incipient-wetness impregnation method. The activity of all catalysts was examined under the temperature range of 573–773 K. The catalytic performance evaluation suggests that Ni content plays a significant role in the Ni dispersion, Ni particle size, and eventually the catalytic activity in HI decomposition. 12% is the optimal Ni content for Ni/AC catalysts in HI decomposition which is balanced between poor dispersion of Ni particles and increasing active center. The results of 24 h durability test, which incorporated with BET and TEM investigations of the 12%Ni/AC catalyst before and after the reaction, indicate that establishing a better Ni particle dispersion pattern and improving the stability of Ni particles on the support should be considered in the future.

  6. Effects of a catalytic volatile particle remover (VPR) on the particulate matter emissions from a direct injection spark ignition engine.

    Science.gov (United States)

    Xu, Fan; Chen, Longfei; Stone, Richard

    2011-10-15

    Emissions of fine particles have been shown to have a large impact on the atmospheric environment and human health. Researchers have shown that gasoline engines, especially direct injection spark ignition (DISI) engines, tend to emit large amounts of small size particles compared to diesel engines fitted with diesel particulate filters (DPFs). As a result, the particle number emissions of DISI engines will be restricted by the forthcoming EU6 legislation. The particulate emission level of DISI engines means that they could face some challenges in meeting the EU6 requirement. This paper is an experimental study on the size-resolved particle number emissions from a spray guided DISI engine and the performance of a catalytic volatile particle remover (VPR), as the EU legislation seeks to exclude volatile particles. The performance of the catalytic VPR was evaluated by varying its temperature and the exhaust residence time. The effect of the catalytic VPR acting as an oxidation catalyst on particle emissions was also tested. The results show that the catalytic VPR led to a marked reduction in the number of particles, especially the smaller size (nucleation mode) particles. The catalytic VPR is essentially an oxidation catalyst, and when post three-way catalyst (TWC) exhaust was introduced to the catalytic VPR, the performance of the catalytic VPR was not affected much by the use of additional air, i.e., no significant oxidation of the PM was observed.

  7. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

    Science.gov (United States)

    Kozuch, Sebastian; Shaik, Sason

    2008-07-03

    A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

  8. Complete determination of the Pin1 catalytic domain thermodynamic cycle by NMR lineshape analysis

    International Nuclear Information System (INIS)

    Greenwood, Alexander I.; Rogals, Monique J.; De, Soumya; Lu, Kun Ping; Kovrigin, Evgenii L.; Nicholson, Linda K.

    2011-01-01

    The phosphorylation-specific peptidyl-prolyl isomerase Pin1 catalyzes the isomerization of the peptide bond preceding a proline residue between cis and trans isomers. To best understand the mechanisms of Pin1 regulation, rigorous enzymatic assays of isomerization are required. However, most measures of isomerase activity require significant constraints on substrate sequence and only yield rate constants for the cis isomer, k cat cis and apparent Michaelis constants, K M App . By contrast, NMR lineshape analysis is a powerful tool for determining microscopic rates and populations of each state in a complex binding scheme. The isolated catalytic domain of Pin1 was employed as a first step towards elucidating the reaction scheme of the full-length enzyme. A 24-residue phosphopeptide derived from the amyloid precurser protein intracellular domain (AICD) phosphorylated at Thr668 served as a biologically-relevant Pin1 substrate. Specific 13 C labeling at the Pin1-targeted proline residue provided multiple reporters sensitive to individual isomer binding and on-enzyme catalysis. We have performed titration experiments and employed lineshape analysis of phosphopeptide 13 C– 1 H constant time HSQC spectra to determine k cat cis , k cat trans , K D cis , and K D trans for the catalytic domain of Pin1 acting on this AICD substrate. The on-enzyme equilibrium value of [E·trans]/[E·cis] = 3.9 suggests that the catalytic domain of Pin1 is optimized to operate on this substrate near equilibrium in the cellular context. This highlights the power of lineshape analysis for determining the microscopic parameters of enzyme catalysis, and demonstrates the feasibility of future studies of Pin1-PPIase mutants to gain insights on the catalytic mechanism of this important enzyme.

  9. Exergy optimization for a novel combination of organic Rankine cycles, Stirling cycle and direct expander turbines

    Science.gov (United States)

    Moghimi, Mahdi; Khosravian, Mohammadreza

    2018-06-01

    In this paper, a novel combination of organic Rankine cycles (ORCs), Stirling cycle and direct expander turbines is modeled and optimized using the genetic algorithm. The Exergy efficiency is considered as an objective function in the genetic algorithm. High efficiency is the main advantage of Stirling cycle, however, it needs nearly isothermal compressor and turbine. Therefore, an argon ORC and a R14 ORC are placed before and after the Striling cycle along with two expander turbines at the end of the line. Each component and cycle of the proposed plant in this article is verified by the previous works available in the literature and good agreement is achieved. The obtained results reveal that 27.98%, 20.86% and 12.90% of the total cold exergy are used by argon ORC, Stirling cycle and R14 ORC, respectively. Therefore, utilization of the Stirling cycle is a good idea for the LNG line cold exergy. The maximum exergy destruction occurs in the heat exchanger after the argon ORC (85.786 kJ/s per one kg/s LNG) due to the wasted cold exergy, which can be used for air conditioning systems in the plant. Finally, it would be shown that the maximum efficiency of the proposed plant is 54.25% and the maximum output power is 355.72 kW.

  10. Exergy optimization for a novel combination of organic Rankine cycles, Stirling cycle and direct expander turbines

    Science.gov (United States)

    Moghimi, Mahdi; Khosravian, Mohammadreza

    2018-01-01

    In this paper, a novel combination of organic Rankine cycles (ORCs), Stirling cycle and direct expander turbines is modeled and optimized using the genetic algorithm. The Exergy efficiency is considered as an objective function in the genetic algorithm. High efficiency is the main advantage of Stirling cycle, however, it needs nearly isothermal compressor and turbine. Therefore, an argon ORC and a R14 ORC are placed before and after the Striling cycle along with two expander turbines at the end of the line. Each component and cycle of the proposed plant in this article is verified by the previous works available in the literature and good agreement is achieved. The obtained results reveal that 27.98%, 20.86% and 12.90% of the total cold exergy are used by argon ORC, Stirling cycle and R14 ORC, respectively. Therefore, utilization of the Stirling cycle is a good idea for the LNG line cold exergy. The maximum exergy destruction occurs in the heat exchanger after the argon ORC (85.786 kJ/s per one kg/s LNG) due to the wasted cold exergy, which can be used for air conditioning systems in the plant. Finally, it would be shown that the maximum efficiency of the proposed plant is 54.25% and the maximum output power is 355.72 kW.

  11. Reversible switching of fluorophore property based on intrinsic conformational transition of adenylate kinase during its catalytic cycle.

    Science.gov (United States)

    Fujii, Akira; Hirota, Shun; Matsuo, Takashi

    2013-07-17

    Adenylate kinase shows a conformational transition (OPEN and CLOSED forms) during substrate binding and product release to mediate the phosphoryl transfer between ADP and ATP/AMP. The protein motional characteristics will be useful to construct switching systems of fluorophore properties caused by the catalytic cycle of the enzyme. This paper demonstrates in situ reversible switching of a fluorophore property driven by the conformational transition of the enzyme. The pyrene-conjugated mutant adenylate kinase is able to switch the monomer/excimer emission property of pyrene on addition of ADP or P(1)P(5)-di(adenosine-5')pentaphosphate (Ap5A, a transition state analog). The observation under the dilute condition (~0.1 μM) indicates that the emission spectral change was caused by the motion of a protein molecule and not led by protein-protein interactions through π-π stacking of pyrene rings. The switching can be reversibly conducted by using hexokinase-coupling reaction. The fashion of the changes in emission intensities at various ligand concentrations is different between ADP, Mg(2+)-bound ADP, and Mg(2+)-bound Ap5A. The emission property switching is repeatable by a sequential addition of a substrate in a one-pot process. It is proposed that the property of a synthetic molecule on the enzyme surface is switchable in response to the catalytic cycle of adenylate kinase.

  12. Direct Catalytic Conversion of Cellulose to 5-Hydroxymethylfurfural Using Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Sanan Eminov

    2016-10-01

    Full Text Available Cellulose is the single largest component of lignocellulosic biomass and is an attractive feedstock for a wide variety of renewable platform chemicals and biofuels, providing an alternative to petrochemicals and petrofuels. This potential is currently limited by the existing methods of transforming this poorly soluble polymer into useful chemical building blocks, such as 5-hydroxymethylfurfural (HMF. Ionic liquids have been used successfully to separate cellulose from the other components of lignocellulosic biomass and so the use of the same medium for the challenging transformation of cellulose into HMF would be highly attractive for the development of the biorefinery concept. In this report, ionic liquids based on 1-butyl-3-methylimidazolium cations [C4C1im]+ with Lewis basic (X = Cl− and Brønsted acidic (X = HSO4− anions were used to investigate the direct catalytic transformation of cellulose to HMF. Variables probed included the composition of the ionic liquid medium, the metal catalyst, and the reaction conditions (temperature, substrate concentration. Lowering the cellulose loading and optimising the temperature achieved a 58% HMF yield after only one hour at 150 °C using a 7 mol % loading of the CrCl3 catalyst. This compares favourably with current literature procedures requiring much longer reactions times or approaches that are difficult to scale such as microwave irradiation.

  13. Selenoglutathione Diselenide: Unique Redox Reactions in the GPx-Like Catalytic Cycle and Repairing of Disulfide Bonds in Scrambled Protein.

    Science.gov (United States)

    Shimodaira, Shingo; Asano, Yuki; Arai, Kenta; Iwaoka, Michio

    2017-10-24

    Selenoglutathione (GSeH) is a selenium analogue of naturally abundant glutathione (GSH). In this study, this water-soluble small tripeptide was synthesized in a high yield (up to 98%) as an oxidized diselenide form, i.e., GSeSeG (1), by liquid-phase peptide synthesis (LPPS). Obtained 1 was applied to the investigation of the glutathione peroxidase (GPx)-like catalytic cycle. The important intermediates, i.e., GSe - and GSeSG, besides GSeO 2 H were characterized by 77 Se NMR spectroscopy. Thiol exchange of GSeSG with various thiols, such as cysteine and dithiothreitol, was found to promote the conversion to GSe - significantly. In addition, disproportionation of GSeSR to 1 and RSSR, which would be initiated by heterolytic cleavage of the Se-S bond and catalyzed by the generated selenolate, was observed. On the basis of these redox behaviors, it was proposed that the heterolytic cleavage of the Se-S bond can be facilitated by the interaction between the Se atom and an amino or aromatic group, which is present at the GPx active site. On the other hand, when a catalytic amount of 1 was reacted with scrambled 4S species of RNase A in the presence of NADPH and glutathione reductase, native protein was efficiently regenerated, suggesting a potential use of 1 to repair misfolded proteins through reduction of the non-native SS bonds.

  14. Approximating maximum weight cycle covers in directed graphs with weights zero and one

    NARCIS (Netherlands)

    Bläser, Markus; Manthey, Bodo

    2005-01-01

    A cycle cover of a graph is a spanning subgraph each node of which is part of exactly one simple cycle. A $k$-cycle cover is a cycle cover where each cycle has length at least $k$. Given a complete directed graph with edge weights zero and one, Max-$k$-DCC(0, 1) is the problem of finding a k-cycle

  15. DIRECT-CYCLE, BOILING-WATER NUCLEAR REACTOR

    Science.gov (United States)

    Harrer, J.M.; Fromm, L.W. Jr.; Kolba, V.M.

    1962-08-14

    A direct-cycle boiling-water nuclear reactor is described that employs a closed vessel and a plurality of fuel assemblies, each comprising an outer tube closed at its lower end, an inner tube, fuel rods in the space between the tubes and within the inner tube. A body of water lying within the pressure vessel and outside the fuel assemblies is converted to saturated steam, which enters each fuel assembly at the top and is converted to superheated steam in the fuel assembly while it is passing therethrough first downward through the space between the inner and outer tubes of the fuel assembly and then upward through the inner tube. (AEC)

  16. Yield optimization in a cycled trickle-bed reactor: ethanol catalytic oxidation as a case study

    Energy Technology Data Exchange (ETDEWEB)

    Ayude, A.; Haure, P. [INTEMA, CONICET, Mar del Plata (Argentina); Cassanello, M. [Universidad de Buenos Aires, PINMATE, Departamento de Industrias, FCEyN, Buenos Aires (Argentina); Martinez, O. [Departamento de Ingenieria Quimica, FI-UNLP-CINDECA, La Plata (Argentina)

    2012-05-15

    The effect of slow ON-OFF liquid flow modulation on the yield of consecutive reactions is investigated for oxidation of aqueous ethanol solutions using a 0.5 % Pd/Al{sub 2}O{sub 3} commercial catalyst in a laboratory trickle-bed reactor. Experiments with modulated liquid flow rate (MLFR) were performed under the same hydrodynamic conditions (degree of wetting, liquid holdup) as experiments with constant liquid flow rate (CLFR). Thus, the impact of the duration of wet and dry cycles as well as the period can be independently investigated. Depending on cycling conditions, acetaldehyde or acetic acid production is favored with MLFR compared to CLFR. Results suggest both the opportunity and challenge of finding a way to tune the cycling parameters for producing the most appropriate product. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Catalytic Enhancement of Carbon Black and Coal-Fueled Hybrid Direct Carbon Fuel Cells

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Ippolito, Davide; Kammer Hansen, Kent

    2015-01-01

    , Ce1-xREExO2-δ (REE = Pr, Sm)) and metal oxides (LiMn2O4, Ag2O). Materials showing the highest activity in carbon black (Mn2O3, CeO2, Ce0.6Pr0.4O2-δ, Ag2O) were subsequently tested for catalytic activity toward bituminous coal, as revealed by both I-V-P curves and electrochemical impedance...... spectroscopy (EIS). Catalytic activity was evaluated as a function of various physical characteristics of doped ceria and manganese-based materials....

  18. Catalytic membrane reactors for tritium recovery from tritiated water in the ITER fuel cycle

    International Nuclear Information System (INIS)

    Tosti, S.; Violante, V.; Basile, A.; Chiappetta, G.; Castelli, S.; De Francesco, M.; Scaglione, S.; Sarto, F.

    2000-01-01

    Palladium and palladium-silver permeators have been obtained by coating porous ceramic tubes with a thin metal layer. Three coating techniques have been studied and characterized: chemical electroless deposition (PdAg film thickness of 10 μm), ion sputtering (about 1 μm) and rolling of thin metal sheets (50 μm). The Pd-ceramic membranes have been used for manufacturing catalytic membrane reactors (CMR) for hydrogen and its isotopes recovering and purifying. These composite membranes and the CMR have been studied and developed for a closed-loop process with reference to the design requirements of the international thermonuclear experimental reactor (ITER) blanket tritium recovery system in the enhanced performance phase of operation. The membranes and CMR have been tested in a pilot plant equipped with temperature, pressure and flow-rate on-line measuring and controlling devices. The conversion value for the water gas shift reaction in the CMR has been measured close to 100% (always above the equilibrium one, 80% at 350 deg. C): the effect of the membrane is very clear since the reaction is moved towards the products because of the continuous hydrogen separation. The rolled thin film membranes have separated the hydrogen from other gases with a complete selectivity and exhibited a slightly larger mass transfer resistance with respect to the electroless membranes. Preliminary tests on the sputtered membranes have also been carried out with a promising performance. Considerations on the use of different palladium alloy in order to improve the performances of the membranes in terms of permeation flux and mechanical strength, such as palladium/yttrium, are also reported

  19. Organic Rankine cycle - review and research directions in engine applications

    Science.gov (United States)

    Panesar, Angad

    2017-11-01

    Waste heat to power conversion using Organic Rankine Cycles (ORC) is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2) are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

  20. ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR; FINAL

    International Nuclear Information System (INIS)

    Robert S. Weber

    1999-01-01

    Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO(sub 2)-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO(sub 2)-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

  1. ADVANCED BYPRODUCT RECOVERY: DIRECT CATALYTIC REDUCTION OF SO2 TO ELEMENTAL SULFUR

    Energy Technology Data Exchange (ETDEWEB)

    Robert S. Weber

    1999-05-01

    Arthur D. Little, Inc., together with its commercialization partner, Engelhard Corporation, and its university partner Tufts, investigated a single-step process for direct, catalytic reduction of sulfur dioxide from regenerable flue gas desulfurization processes to the more valuable elemental sulfur by-product. This development built on recently demonstrated SO{sub 2}-reduction catalyst performance at Tufts University on a DOE-sponsored program and is, in principle, applicable to processing of regenerator off-gases from all regenerable SO{sub 2}-control processes. In this program, laboratory-scale catalyst optimization work at Tufts was combined with supported catalyst formulation work at Engelhard, bench-scale supported catalyst testing at Arthur D. Little and market assessments, also by Arthur D. Little. Objectives included identification and performance evaluation of a catalyst which is robust and flexible with regard to choice of reducing gas. The catalyst formulation was improved significantly over the course of this work owing to the identification of a number of underlying phenomena that tended to reduce catalyst selectivity. The most promising catalysts discovered in the bench-scale tests at Tufts were transformed into monolith-supported catalysts at Engelhard. These catalyst samples were tested at larger scale at Arthur D. Little, where the laboratory-scale results were confirmed, namely that the catalysts do effectively reduce sulfur dioxide to elemental sulfur when operated under appropriate levels of conversion and in conditions that do not contain too much water or hydrogen. Ways to overcome those limitations were suggested by the laboratory results. Nonetheless, at the end of Phase I, the catalysts did not exhibit the very stringent levels of activity or selectivity that would have permitted ready scale-up to pilot or commercial operation. Therefore, we chose not to pursue Phase II of this work which would have included further bench-scale testing

  2. Pyroelectrically Induced Pyro-Electro-Chemical Catalytic Activity of BaTiO3 Nanofibers under Room-Temperature Cold–Hot Cycle Excitations

    OpenAIRE

    Yuntao Xia; Yanmin Jia; Weiqi Qian; Xiaoli Xu; Zheng Wu; Zichen Han; Yuanting Hong; Huilin You; Muhammad Ismail; Ge Bai; Liwei Wang

    2017-01-01

    A pyro-electro-chemical catalytic dye decomposition using lead-free BaTiO3 nanofibers was realized under room-temperature cold–hot cycle excitation (30–47 °C) with a high Rhodamine B (RhB) decomposition efficiency ~99%, which should be ascribed to the product of pyro-electric effect and electrochemical redox reaction. Furthermore, the existence of intermediate product of hydroxyl radical in pyro-electro-chemical catalytic process was also observed. There is no significant decrease in pyro-ele...

  3. Efficient catalytic system for the direct transformation of lignocellulosic biomass to furfural and 5-hydroxymethylfurfural.

    Science.gov (United States)

    Zhang, Luxin; Xi, Guoyun; Zhang, Jiaxin; Yu, Hongbing; Wang, Xiaochang

    2017-01-01

    A feasible approach was developed for the co-production of 5-hydroxymethylfurfural (5-HMF) and furfural from corncob via a new porous polytriphenylamine-SO 3 H (SPTPA) solid acid catalyst in lactone solvents. XRD, SEM, XPS, N 2 adsorption-desorption, elemental analysis, TG-DTA, acid-base titration and FTIR spectroscopy techniques were used to characterize the catalyst. This study demonstrates and optimizes the catalytic performance of SPTPA and solvent selection. SPTPA was found to exhibit superior catalytic ability in γ-valerolactone (GVL). Under the optimum reaction conditions, simultaneously encouraging yields of furfural (73.9%) and 5-HMF (32.3%) were achieved at 448K. The main advantages of this process include reasonable yields of both 5-HMF and furfural in the same reaction system, practical simplicity for the raw biomass utilization, and the use of a safe and environmentally benign solvent. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges

    Science.gov (United States)

    Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M.; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H.

    2014-01-01

    Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp2 carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations. PMID:25331874

  5. Performance and Economics of Catalytic Glow Plugs and Shields in Direct Injection Natural Gas Engines for the Next Generation Natural Gas Vehicle Program: Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Mello, J. P.; Bezaire, D.; Sriramulu, S.; Weber, R.

    2003-08-01

    Subcontractor report details work done by TIAX and Westport to test and perform cost analysis for catalytic glow plugs and shields for direct-injection natural gas engines for the Next Generation Natural Gas Vehicle Program.

  6. Life Cycle Assessment Applied to Naphtha Catalytic Reforming Analyse de cycle de vie appliquée au reformage catalytique du naphta

    Directory of Open Access Journals (Sweden)

    Portha J.-F.

    2010-10-01

    Full Text Available Facing the increase of environmental concerns in the oil and gas industry, engineers and scientists need information to assess sustainability of chemical processes. Among the different methods available, Life Cycle Assessment (LCA is widely used. In this study, LCA is applied to a catalytic reforming process using the Eco- Indicator 99 as life cycle impact assessment method. The main identified environmental impacts are fossil fuels consumption, climate change and respiratory effects due to inorganics compounds. The influence of different process parameters (feed composition, reaction temperature is determined with respect to environmental impacts. Two allocation methods are analysed (mass and exergetic allocation and two different process versions are compared in order to determine the effect of some improvements on environmental impact. Les considérations liées à l’environnement doivent de plus en plus être prises en compte par les ingénieurs et les scientifiques afin de juger de la durabilité des procédés chimiques dans l’industrie pétrolière et gazière. Parmi les différentes méthodes d’analyse environnementale, l’Analyse de Cycle de Vie (ACV est très utilisée. Dans cette étude, l’ACV est appliquée au procédé de reformage catalytique du naphta en utilisant la méthode Eco-Indicateur 99 comme méthode d’analyse des impacts du cycle de vie. Les principaux impacts environnementaux du procédé sont la consommation de combustibles fossiles, le changement climatique et les effets sur la respiration liés aux composés organiques. L’influence de différents paramètres (composition de l’alimentation, température de réaction sur les impacts environnementaux est testée. Deux méthodes d’allocation sont analysées (allocation massique et énergétique et deux versions du procédé de reformage catalytique sont comparées afin de déterminer les améliorations possibles permettant de minimiser les impacts.

  7. Directed evolution of a β-mannanase from Rhizomucor miehei to improve catalytic activity in acidic and thermophilic conditions.

    Science.gov (United States)

    Li, Yan-Xiao; Yi, Ping; Yan, Qiao-Juan; Qin, Zhen; Liu, Xue-Qiang; Jiang, Zheng-Qiang

    2017-01-01

    β-Mannanase randomly cleaves the β-1,4-linked mannan backbone of hemicellulose, which plays the most important role in the enzymatic degradation of mannan. Although the industrial applications of β-mannanase have tremendously expanded in recent years, the wild-type β-mannanases are still defective for some industries. The glycoside hydrolase (GH) family 5 β-mannanase ( Rm Man5A) from Rhizomucor miehei shows many outstanding properties, such as high specific activity and hydrolysis property. However, owing to the low catalytic activity in acidic and thermophilic conditions, the application of Rm Man5A to the biorefinery of mannan biomasses is severely limited. To overcome the limitation, Rm Man5A was successfully engineered by directed evolution. Through two rounds of screening, a mutated β-mannanase (m Rm Man5A) with high catalytic activity in acidic and thermophilic conditions was obtained, and then characterized. The mutant displayed maximal activity at pH 4.5 and 65 °C, corresponding to acidic shift of 2.5 units in optimal pH and increase by 10 °C in optimal temperature. The catalytic efficiencies ( k cat / K m ) of m Rm Man5A towards many mannan substrates were enhanced more than threefold in acidic and thermophilic conditions. Meanwhile, the high specific activity and excellent hydrolysis property of Rm Man5A were inherited by the mutant m Rm Man5A after directed evolution. According to the result of sequence analysis, three amino acid residues were substituted in m Rm Man5A, namely Tyr233His, Lys264Met, and Asn343Ser. To identify the function of each substitution, four site-directed mutations (Tyr233His, Lys264Met, Asn343Ser, and Tyr233His/Lys264Met) were subsequently generated, and the substitutions at Tyr233 and Lys264 were found to be the main reason for the changes of m Rm Man5A. Through directed evolution of Rm Man5A, two key amino acid residues that controlled its catalytic efficiency under acidic and thermophilic conditions were identified

  8. Reduction of light cycle oil in catalytic cracking of bitumen-derived crude HGOs through catalyst selection

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Fuchen; Xu, Chunming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, 102200 (China); Ng, Siauw H. [National Centre for Upgrading Technology, 1 Oil Patch Drive, Suite A202, Devon, Alberta (Canada); Yui, Sok [Syncrude Research Centre, 9421-17 Avenue, Edmonton, Alberta (Canada)

    2007-09-15

    In an attempt to reduce the production of light cycle oil (LCO), a non-premium fluid catalytic cracking (FCC) product in North America, a large-pore catalyst containing rare-earth-exchanged Y (REY) zeolite, was used to crack two Canadian bitumen-derived crude heavy gas oils (HGOs) hydrotreated to different extents. For comparison, a regular equilibrium FCC catalyst with ultra-stable Y (USY) zeolite and a conventional western Canadian crude HGO were also included in the study. Cracking experiments were conducted in a fixed-bed microactivity test (MAT) reactor at 510 C, 30 s oil injection time, and varying catalyst-to-oil ratios for different conversions. The results show that pre-cracking of heavy molecules with wide-pore matrix, followed by zeolite cracking, enhanced conversion at the expense of light and heavy cycle oils at a constant catalyst-to-oil ratio, giving improved product selectivities (e.g., higher gasoline and lower dry gas, LCO, and coke yields, in general, at a given conversion). To systematically assess the benefits of employing the specialty catalyst over the regular catalyst in cracking Canadian HGOs, individual product yields were compared at common bases, including constant catalyst-to-oil ratios, conversions, and coke yields for three feeds, and at maximum gasoline yield for one feed. In most cases, the preferred choice of large-pore zeolite-rich catalyst over its counterpart was evident. The observed cracking phenomena were explained based on properties of catalysts and characterization data of feedstocks, including their hydrocarbon type analyses by gas chromatograph with a mass-selective detector (GC-MSD). (author)

  9. Can cycling safety be improved by opening all unidirectional cycle paths for cycle traffic in both directions? A theoretical examination of available literature and data.

    Science.gov (United States)

    Methorst, Rob; Schepers, Paul; Kamminga, Jaap; Zeegers, Theo; Fishman, Elliot

    2017-08-01

    Many studies have found bicycle-motor vehicle crashes to be more likely on bidirectional cycle paths than on unidirectional cycle paths because drivers do not expect cyclists riding at the right side of the road. In this paper we discuss the hypothesis that opening all unidirectional cycle paths for cycle traffic in both directions prevent this lack of expectancy and accordingly improves cycling safety. A new national standard requires careful consideration because a reversal is difficult once cyclists are used to their new freedom of route choice. We therefore explored the hypothesis using available data, research, and theories. The results show that of the length of cycle paths along distributor roads in the Netherlands, 72% is bidirectional. If drivers would become used to cyclists riding at the left side of the road, this result raises the question of why bidirectional cycle paths in the Netherlands still have a poor safety record compared to unidirectional cycle paths. Moreover, our exploration suggested that bidirectional cycle paths have additional safety problems. It increases the complexity of unsignalized intersections because drivers have to scan more directions in a short period of time. Moreover, there are some indications that the likelihood of frontal crashes between cyclists increases. We reject the hypothesis that opening all unidirectional cycle paths for cycle traffic in both directions will improve cycle safety. We recommend more attention for mitigating measures given the widespread application of bidirectional cycle paths in the Netherlands. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Key Feature of the Catalytic Cycle of TNF-α Converting Enzyme Involves Communication Between Distal Protein Sites and the Enzyme Catalytic Core

    International Nuclear Information System (INIS)

    Solomon, A.; Akabayov, B.; Frenkel, A.; Millas, M.; Sagi, I.

    2007-01-01

    Despite their key roles in many normal and pathological processes, the molecular details by which zinc-dependent proteases hydrolyze their physiological substrates remain elusive. Advanced theoretical analyses have suggested reaction models for which there is limited and controversial experimental evidence. Here we report the structure, chemistry and lifetime of transient metal-protein reaction intermediates evolving during the substrate turnover reaction of a metalloproteinase, the tumor necrosis factor-α converting enzyme (TACE). TACE controls multiple signal transduction pathways through the proteolytic release of the extracellular domain of a host of membrane-bound factors and receptors. Using stopped-flow x-ray spectroscopy methods together with transient kinetic analyses, we demonstrate that TACE's catalytic zinc ion undergoes dynamic charge transitions before substrate binding to the metal ion. This indicates previously undescribed communication pathways taking place between distal protein sites and the enzyme catalytic core. The observed charge transitions are synchronized with distinct phases in the reaction kinetics and changes in metal coordination chemistry mediated by the binding of the peptide substrate to the catalytic metal ion and product release. Here we report key local charge transitions critical for proteolysis as well as long sought evidence for the proposed reaction model of peptide hydrolysis. This study provides a general approach for gaining critical insights into the molecular basis of substrate recognition and turnover by zinc metalloproteinases that may be used for drug design

  11. Catalysis looks to the future. Panel on new directions in catalytic science and technology

    Energy Technology Data Exchange (ETDEWEB)

    1992-12-31

    Catalysts play a vital role in providing society with fuels, commodity and fine chemicals, pharmaceuticals, and means for protecting the environment. To be useful, a good catalyst must have a high turnover frequency (activity), produce the right kind of product (selectivity), and have a long life (durability), all at an acceptable cost. Research in the field of catalysis provides the tools and understanding required to facilitate and accelerate the development of improved catalysts and to open opportunities for the discovery of new catalytic processes. The aim of this report is to identify the research opportunities and challenges for catalysis in the coming decades and to detail the resources necessary to ensure steady progress. Chapter 2 discusses opportunities for developing new catalysts to meet the demands of the chemical and fuel industries, and the increasing role of catalysis in environmental protection. The intellectual challenges for advancing the frontiers of catalytic science are outlined in Chapter 3. The human and institutional resources available in the US for carrying out research on catalysis are summarized in Chapter 4. The findings and recommendations of the panel for industry, academe, the national laboratories, and the federal government are presented in Chapter 5.

  12. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    International Nuclear Information System (INIS)

    Li, Hu; Govind, Khokarale Santosh; Kotni, Ramakrishna; Shunmugavel, Saravanamurugan; Riisager, Anders; Yang, Song

    2014-01-01

    Graphical abstract: Catalytic conversion of carbohydrates into HMF and EMF in ethanol/DMSO with acid–base bifunctional hybrid nanospheres prepared from self-assembly of corresponding basic amino acids and HPA. - Highlights: • Acid–base bifunctional nanospheres were efficient for production of EMF from sugars. • Synthesis of EMF in a high yield of 76.6% was realized from fructose. • Fructose based biopolymers could also be converted into EMF with good yields. • Ethyl glucopyranoside was produced in good yields from glucose in ethanol. - Abstract: A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity

  13. Environmental macroeconomics : Environmental policy, business cycles, and directed technical change

    NARCIS (Netherlands)

    Fischer, Carolyn; Heutel, Garth

    Environmental economics has traditionally fallen in the domain of microeconomics, but approaches from macroeconomics have recently been applied to studying environmental policy. We focus on two macroeconomic tools and their application to environmental economics. First, real-business-cycle models

  14. Preparation and electrochemistry of Pd-Ni/Si nanowire nanocomposite catalytic anode for direct ethanol fuel cell.

    Science.gov (United States)

    Miao, Fengjuan; Tao, Bairui; Chu, Paul K

    2012-04-28

    A new silicon-based anode suitable for direct ethanol fuel cells (DEFCs) is described. Pd-Ni nanoparticles are coated on Si nanowires (SiNWs) by electroless co-plating to form the catalytic materials. The electrocatalytic properties of the SiNWs and ethanol oxidation on the Pd-Ni catalyst (Pd-Ni/SiNWs) are investigated electrochemically. The effects of temperature and working potential limit in the anodic direction on ethanol oxidation are studied by cyclic voltammetry. The Pd-Ni/SiNWs electrode exhibits higher electrocatalytic activity and better long-term stability in an alkaline solution. It also yields a larger current density and negative onset potential thus boding well for its application to fuel cells. This journal is © The Royal Society of Chemistry 2012

  15. A Simple Catalytic Mechanism for the Direct Coupling of α-Carbonyls with Functionalized Amines: A One-Step Synthesis of Plavix

    OpenAIRE

    Evans, Ryan W.; Zbieg, Jason R.; Zhu, Shaolin; Li, Wei; MacMillan, David W. C.

    2013-01-01

    The direct α-amination of ketones, esters, and aldehydes has been accomplished via copper catalysis. In the presence of catalytic copper(II) bromide, a diverse range of carbonyl and amine substrates undergo fragment coupling to produce synthetically useful α-amino substituted motifs. The transformation is proposed to proceed via a catalytically generated α-bromo carbonyl species; nucleophilic displacement of the bromide by the amine then delivers the α-amino carbonyl adduct while the catalyst...

  16. Performance and life cycle environmental benefits of recycling spent ion exchange brines by catalytic treatment of nitrate.

    Science.gov (United States)

    Choe, Jong Kwon; Bergquist, Allison M; Jeong, Sangjo; Guest, Jeremy S; Werth, Charles J; Strathmann, Timothy J

    2015-09-01

    Salt used to make brines for regeneration of ion exchange (IX) resins is the dominant economic and environmental liability of IX treatment systems for nitrate-contaminated drinking water sources. To reduce salt usage, the applicability and environmental benefits of using a catalytic reduction technology to treat nitrate in spent IX brines and enable their reuse for IX resin regeneration were evaluated. Hybrid IX/catalyst systems were designed and life cycle assessment of process consumables are used to set performance targets for the catalyst reactor. Nitrate reduction was measured in a typical spent brine (i.e., 5000 mg/L NO3(-) and 70,000 mg/L NaCl) using bimetallic Pd-In hydrogenation catalysts with variable Pd (0.2-2.5 wt%) and In (0.0125-0.25 wt%) loadings on pelletized activated carbon support (Pd-In/C). The highest activity of 50 mgNO3(-)/(min - g(Pd)) was obtained with a 0.5 wt%Pd-0.1 wt%In/C catalyst. Catalyst longevity was demonstrated by observing no decrease in catalyst activity over more than 60 days in a packed-bed reactor. Based on catalyst activity measured in batch and packed-bed reactors, environmental impacts of hybrid IX/catalyst systems were evaluated for both sequencing-batch and continuous-flow packed-bed reactor designs and environmental impacts of the sequencing-batch hybrid system were found to be 38-81% of those of conventional IX. Major environmental impact contributors other than salt consumption include Pd metal, hydrogen (electron donor), and carbon dioxide (pH buffer). Sensitivity of environmental impacts of the sequencing-batch hybrid reactor system to sulfate and bicarbonate anions indicate the hybrid system is more sustainable than conventional IX when influent water contains reuse cycles. The study showed that hybrid IX/catalyst reactor systems have potential to reduce resource consumption and improve environmental impacts associated with treating nitrate-contaminated water sources. Copyright © 2015 Elsevier Ltd. All rights

  17. Advanced byproduct recovery: Direct catalytic reduction of sulfur dioxide to elemental sulfur. Quarterly report, April 1--June 30, 1997

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The team of Arthur D. Little, Tufts University and Engelhard Corporation are conducting Phase 1 of a four and a half year, two-phase effort to develop and scale-up an advanced byproduct recovery technology that is a direct, single-stage, catalytic process for converting sulfur dioxide to elemental sulfur. This catalytic process reduces SO{sub 2} over a fluorite-type oxide (such as ceria and zirconia). The catalytic activity can be significantly promoted by active transition metals, such as copper. More than 95% elemental sulfur yield, corresponding to almost complete sulfur dioxide conversion, was obtained over a Cu-Ce-O oxide catalyst as part of an on-going DOE-sponsored, University Coal Research Program. This type of mixed metal oxide catalyst has stable activity, high selectivity for sulfur production, and is resistant to water and carbon dioxide poisoning. Tests with CO and CH{sub 4} reducing gases indicate that the catalyst has the potential for flexibility with regard to the composition of the reducing gas, making it attractive for utility use. The performance of the catalyst is consistently good over a range of SO{sub 2} inlet concentration (0.1 to 10%) indicating its flexibility in treating SO{sub 2} tail gases as well as high concentration streams. The principal objective of the Phase 1 program is to identify and evaluate the performance of a catalyst which is robust and flexible with regard to choice of reducing gas. In order to achieve this goal, the authors have planned a structured program including: Market/process/cost/evaluation; Lab-scale catalyst preparation/optimization studies; Lab-scale, bulk/supported catalyst kinetic studies; Bench-scale catalyst/process studies; and Utility review. Progress is reported from all three organizations.

  18. Population exposure from the fuel cycle: Review and future direction

    International Nuclear Information System (INIS)

    Richmond, C.R.

    1987-01-01

    The legacy of radiation exposures confronting man arises from two historical sources of energy, the sun and radioactive decay. Contemporary man continues to be dependent on these two energy sources, which include the nuclear fuel cycle. Radiation exposures from all energy sources should be examined, with particular emphasis on the nuclear fuel cycle, incidents such as Chernobyl and Three Mile Island. In addition to risk estimation, concepts such as de minimis, life shortening as a measure of risk, and competing risks as projected into the future must be considered in placing radiation exposures in perspective. The utility of these concepts is in characterizing population exposures for decision makers in a manner that the public may judge acceptable. All these viewpoints are essential in the evaluation of population exposure from the nuclear fuel cycle

  19. Solar reforming of methane in a direct absorption catalytic reactor on a parabolic dish. 2: Modeling and analysis

    Science.gov (United States)

    Skocypec, Russell D.; Hogan, Roy E., Jr.; Muir, James F.

    1991-01-01

    The catalytically enhanced solar absorption receiver (CAESAR) experiment was conducted to determine the thermal, chemical, and mechanical performance of a commercial-scale, dish-mounted, direct catalytic absorption receiver (DCAR) reactor over a range of steady state and transient (cloud) operating conditions. The focus of the experiment is on global performance such as receiver efficiencies and overall methane conversion; it was not intended to provide data for code validation. A numerical model was previously developed to provide guidance in the design of the absorber. The one-dimensional, planar and steady-state model incorporates, the following energy transfer mechanisms: solar and infrared radiation, heterogeneous chemical reaction, conduction in the solid phase, and convection between the fluid and solid phases. A number of upgrades to the model and improved property values are presented here. Model predictions are shown to bound the experimental axial thermocouple data when experimental uncertainties are included. Global predictions are made using a technique in which the incident solar flux distribution is subdivided into flux contour bands. Model predictions for each band are then spatially integrated to provide global predictions such as reactor efficiencies and methane conversions. Global predictions are shown to compare well with experimental data. Reactor predictions for anticipated operating conditions suggest a further decrease in optical density at the front of the absorber inner disk may be beneficial. The need to conduct code-validation experiments is identified as being essential in improving the confidence in the capability to predict large-scale reactor operation.

  20. Direct liquefaction of wood through solvolysis and catalytic hydrodeoxygenation: an engineering assessment

    Energy Technology Data Exchange (ETDEWEB)

    Moffat, J.M.; Overend, J.P.

    1985-01-01

    Liquefaction of wood to produce fuel and chemical intermediates has been intensively studied over the last decade. The results of Canadian research into process feasibility are presented on the basis of two studies, the first in 1980 utilizing data of the mid-70s and the other on the basis of research conducted up to 1982. The earlier study was for a single reactor concept in which catalyst, wood and hydrogen were reacted to produce a proto-oil, while the later study embodies a two-stage concept involving dissolution of the polymer matrix followed by fractionation and catalytic upgrading using hydrodeoxygenation. Increased knowledge of the characteristics of the first stage products show that there are many component mixtures containing between 10 and 20% oxygen. Most of the oxygen is in aromatic phenol-type structures with some ether linkages, and low severity processes to deoxygenate the product while increasing the hydrogen to carbon ratio are called for. The economic prospects for a two-stage process are described on the basis of a hydrocarbon process proposed by HRI International for Kraft process lignin. These show that a mix of BTX products and fuel oil could generate a profitable rate of return. 62 references.

  1. Direct observation of doping incorporation pathways in self-catalytic GaMnAs nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Kasama, T., E-mail: tk@cen.dtu.dk; Yazdi, S. [Center for Electron Nanoscopy, Technical University of Denmark, DK-2800 Kongens Lyngby (Denmark); Thuvander, M. [Department of Applied Physics, Chalmers University of Technology, SE-41296 Gothenburg (Sweden); Siusys, A. [Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, PL-02-668 Warszawa (Poland); Gontard, L. C. [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), C/Américo Vespucio 49, 41092 Seville (Spain); Kovács, A.; Duchamp, M.; Dunin-Borkowski, R. E. [Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Jülich, D-52425 Jülich (Germany); Gustafsson, A. [Solid State Physics and the Nanometer Structure Consortium, Lund University, P.O. Box 118, SE-221 00 Lund (Sweden); Sadowski, J. [Institute of Physics, Polish Academy of Sciences, al. Lotników 32/46, PL-02-668 Warszawa (Poland); MAX-IV Laboratory, Lund University, P.O. Box 118, SE-221 00 Lund (Sweden)

    2015-08-07

    Doping mechanisms of Mn in GaAs nanowires (NWs) that have been grown self-catalytically at 600 °C by molecular beam epitaxy (MBE) are investigated using advanced electron microscopy techniques and atom probe tomography. Mn is found to be incorporated primarily in the form of non-magnetic tetragonal Ga{sub 0.82}Mn{sub 0.18} nanocrystals in Ga catalyst droplets at the ends of the NWs, while trace amounts of Mn (22 ± 4 at. ppm) are also distributed randomly in the NW bodies without forming clusters or precipitates. The nanocrystals are likely to form after switching off the reaction in the MBE chamber, since they are partially embedded in neck regions of the NWs. The Ga{sub 0.82}Mn{sub 0.18} nanocrystals and the low Mn concentration in the NW bodies are insufficient to induce a ferromagnetic phase transition, suggesting that it is difficult to have high Mn contents in GaAs even in 1-D NW growth via the vapor-liquid-solid process.

  2. Future directions and cycles for electricity production from geothermal resources

    International Nuclear Information System (INIS)

    Michaelides, Efstathios E.

    2016-01-01

    Graphical abstract: 25% more power may be produced using binary-flashing geothermal cycles. - Highlights: • Power from geothermal power plants is continuously available and “dispatchable.” • The next generation of geothermal will include more binary plants. • Lower temperature geothermal resources will be utilized in the future. • Dry rock resources may produce a high fraction of electricity in several countries. - Abstract: Geothermal power production is economically competitive and capable to produce a high percentage of the electric power demand in several countries. The currently operating geothermal power plants utilize water from an aquifer at relatively higher temperatures and produce power using dry steam, flashing or binary cycles. A glance at the map of the global geothermal resources proves that there is a multitude of sites, where the aquifer temperature is lower. There are also many geothermal resources where a high geothermal gradient exists in the absence of an aquifer. It becomes apparent that the next generation of geothermal power plants will utilize more of the lower-temperature aquifer resources or the dry resources. For such power plants to be economically competitive, modified or new cycles with higher efficiencies must be used. This paper presents two methods to increase the efficiency of the currently used geothermal cycles. The first uses a binary-flashing system to reduce the overall entropy production, thus, producing more electric power from the resource. The second describes a heat extraction system to be used with dry hot-rock resources.

  3. Pyroelectrically Induced Pyro-Electro-Chemical Catalytic Activity of BaTiO3 Nanofibers under Room-Temperature Cold–Hot Cycle Excitations

    Directory of Open Access Journals (Sweden)

    Yuntao Xia

    2017-04-01

    Full Text Available A pyro-electro-chemical catalytic dye decomposition using lead-free BaTiO3 nanofibers was realized under room-temperature cold–hot cycle excitation (30–47 °C with a high Rhodamine B (RhB decomposition efficiency ~99%, which should be ascribed to the product of pyro-electric effect and electrochemical redox reaction. Furthermore, the existence of intermediate product of hydroxyl radical in pyro-electro-chemical catalytic process was also observed. There is no significant decrease in pyro-electro-chemical catalysis activity after being recycled five times. The pyro-electrically induced pyro-electro-chemical catalysis provides a high-efficient, reusable and environmentally friendly technology to remove organic pollutants from water.

  4. The catalytic potency of ß-glucosidase from Pyroccus furiosus in the direct glucosylation reaction

    NARCIS (Netherlands)

    Roode, de B.M.; Meer, van der T.D.; Kaper, T.; Franssen, M.C.R.; Padt, van der A.; Oost, van der J.; Boom, R.M.

    2001-01-01

    Enzymes from extremophiles operate at conditions that are different from their `normal' counterparts, and are therefore a useful extension of the enzyme toolbox. In this paper, the direct glucosylation reaction mediated by a hyperthermophilic -glucosidase from Pyrocuccus furiosus was investigated.

  5. Catalytic carbene transfer allows the direct customization of cyclic purine dinucleotides.

    Science.gov (United States)

    Fei, Na; Häussinger, Daniel; Blümli, Seraina; Laventie, Benoît-Joseph; Bizzini, Lorenzo D; Zimmermann, Kaspar; Jenal, Urs; Gillingham, Dennis

    2014-08-11

    We describe a simple method for the direct modification of nucleobases in cyclic purine dinucleotides, important signalling molecules in both prokaryotes and eukaryotes. The method tolerates all members of the cyclic dinucleotide family and could be used to modulate their function or introduce useful side-chains such as fluorophores and photo-crosslinking groups.

  6. Chronic fluoxetine treatment directs energy metabolism towards the citric acid cycle and oxidative phosphorylation in rat hippocampal nonsynaptic mitochondria.

    Science.gov (United States)

    Filipović, Dragana; Costina, Victor; Perić, Ivana; Stanisavljević, Andrijana; Findeisen, Peter

    2017-03-15

    Fluoxetine (Flx) is the principal treatment for depression; however, the precise mechanisms of its actions remain elusive. Our aim was to identify protein expression changes within rat hippocampus regulated by chronic Flx treatment versus vehicle-controls using proteomics. Fluoxetine-hydrohloride (15mg/kg) was administered daily to adult male Wistar rats for 3weeks, and cytosolic and nonsynaptic mitochondrial hippocampal proteomes were analyzed. All differentially expressed proteins were functionally annotated according to biological process and molecular function using Uniprot and Blast2GO. Our comparative study revealed that in cytosolic and nonsynaptic mitochondrial fractions, 60 and 3 proteins respectively, were down-regulated, and 23 and 60 proteins, respectively, were up-regulated. Proteins differentially regulated in cytosolic and nonsynaptic mitochondrial fractions were primarily related to cellular and metabolic processes. Of the identified proteins, the expressions of calretinin and parvalbumine were confirmed. The predominant molecular functions of differentially expressed proteins in both cell hippocampal fractions were binding and catalytic activity. Most differentially expressed proteins in nonsynaptic mitochondria were catalytic enzymes involved in the pyruvate metabolism, citric acid cycle, oxidative phosphorylation, ATP synthesis, ATP transduction and glutamate metabolism. Results indicate that chronic Flx treatment may influence proteins involved in calcium signaling, cytoskeletal structure, chaperone system and stimulates energy metabolism via the upregulation of GAPDH expression in cytoplasm, as well as directing energy metabolism toward the citric acid cycle and oxidative phosphorylation in nonsynaptic mitochondria. This approach provides new insight into the chronic effects of Flx treatment on protein expression in a key brain region associated with stress response and memory. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. THE DIMINISHING OF THE CONTENT OF TEXTILE DIRECT DYES AND AUXILIARY COMPOUNDS DURING THEIR CATALYTIC OXIDATION

    Directory of Open Access Journals (Sweden)

    Maria Gonta

    2014-06-01

    Full Text Available Advanced oxidation methods of organic compounds lead to their partial mineralization and increase of the adsorption process efficiency on the surface of oxidized activated carbon. We have studied the oxidation process using model solutions containing mixture of dye direct brown (DB, ethylene glycol (EGL and sodium lauryl sulfate (SLS under the action of Fenton reagent, in the presence and absence of UV irradiation or under the action of electric current (in the electrochemical cell. The same studies were performed by replacing the iron (II ion with titanium dioxide.

  8. Actual characteristics study on HTR-10GT coupling with direct gas turbine cycle

    International Nuclear Information System (INIS)

    Peng Xuechuang; Zhu Shutang; Wang Jie

    2005-01-01

    Compared with a plant of steam turbine cycle, a HTGR plant with direct gas turbine cycle has a higher thermal efficiency. A lot of investigations on the characteristics of HTR-10GT, which is the reactor studying project of Tsinghua University, have been carried out, however, all of them are based on the theoretical Brayton Cycle which neglects many actual conditions, such as leakage, pressure loss and so on. For engineering practices, leakage is an unavoidable problem. The difference of the location and capacity of leakage will directly influence the working medium's thermoparameters and lead to fall of the cycle efficiency. The present study is focused on the performance of an actual Brayton cycle with practical conditions of leakage. The present study which based on building the physical and mathematical model of the leakage, aims to study the actual characteristics of the direct gas turbine circle. (authors)

  9. Actual characteristics study on HTR-10GT coupling with direct gas turbine cycle

    International Nuclear Information System (INIS)

    Peng Xuechuang; Zhu Shutang; Wang Jie

    2005-01-01

    HTR-10GT is a testing project coupling the reactor HTR-10 with direct gas turbine cycle. Its thermal cycle can be taken as a closed, recuperated and inter-cooled Brayton cycle. The present study is focused on the thermal cycle performance of HTR-10GT under practical conditions of leakage, pressure losses, etc.. Through thermodynamic analysis, the expression of cycle efficiency for actual thermal cycle is derived. By establishing a physical model with friction loss and leakage, a set of governing equation are constructed based on some reasonable assumptions. The results of actual cycle efficiency have been calculated for different leakage amount at different locations while the effects of leakage under different power level have also been calculated and analyzed. (authors)

  10. Direct catalytic conversion of brown seaweed-derived alginic acid to furfural using 12-tungstophosphoric acid catalyst in tetrahydrofuran/water co-solvent

    International Nuclear Information System (INIS)

    Park, Geonu; Jeon, Wonjin; Ban, Chunghyeon; Woo, Hee Chul; Kim, Do Heui

    2016-01-01

    Highlights: • Furfural was produced by catalytic conversion of macroalgae-derived alginic acid. • 12-Tungstophosphoric acid (H_3PW_1_2O_4_0) showed remarkable catalytic performance. • Tetrahydrofuran (THF) as a reaction medium significantly enhanced production of furfural. - Abstract: Furfural, a biomass-derived platform chemical, was produced by acid-catalyzed reaction of alginic acid extracted from brown seaweed. Three acid catalysts, H_2SO_4, Amberlyst15 and 12-tungstophosphoric acid (H_3PW_1_2O_4_0), were compared to evaluate their catalytic performance for the alginic acid conversion. The H_3PW_1_2O_4_0 catalyst showed the highest catalytic activity, yielding the maximum furfural yield (33.8%) at 180 °C for 30 min in tetrahydrofuran/water co-solvent. Higher reaction temperature promoted the conversion of alginic acid to furfural, but the transformation of furfural to humin was also accelerated. To our knowledge, this is the highest furfural yield among studies about the direct catalytic conversion of alginic acid. Furthermore, products distribution with time-on-stream was investigated in detail, which led us to propose a reaction pathway.

  11. Dynamics of a small direct cycle pebble bed HTR

    International Nuclear Information System (INIS)

    Verkerk, E.C.; Heek, A.I. van

    2001-01-01

    The Dutch market for combined generation of heat and power identifies a unit size of 40 MW thermal for the conceptual design of a nuclear cogeneration plant. The ACACIA system provides 14 MW(e) electricity combined with 17 t/h of high temperature steam (220 deg. C, 10 bar) with a pebble bed high temperature reactor directly coupled with a helium compressor and a helium turbine. To come to quantitative statements about the ACACIA transient behaviour, a calculational coupling between the high temperature reactor core analysis code package Panthermix (Panther-Thermix/Direkt) and the thermal hydraulic code RELAP5 for the energy conversion system has been made. This paper will present the analysis of safety related transients. The usual incident scenarios Loss of Coolant Incident (LOCI) and Loss of Flow Incident (LOFI) have been analysed. Besides, also a search for the real maximum fuel temperature (inside a fuel pebble anywhere in the core) has been made. It appears that the maximum fuel temperatures are not reached during a LOFI or LOCI with a halted mass flow rate, but for situations with a small mass flow rate, 1-0.5%. As such, a LOFI or LOCI does not represent the worst-case scenario in terms of maximal fuel temperature. (author)

  12. Integration between direct steam generation in linear solar collectors and supercritical carbon dioxide Brayton power cycles

    OpenAIRE

    Coco Enríquez, Luis; Muñoz Antón, Javier; Martínez-Val Peñalosa, José María

    2015-01-01

    Direct Steam Generation in Parabolic Troughs or Linear Fresnel solar collectors is a technology under development since beginning of nineties (1990's) for replacing thermal oils and molten salts as heat transfer fluids in concentrated solar power plants, avoiding environmental impacts. In parallel to the direct steam generation technology development, supercritical Carbon Dioxide Brayton power cycles are maturing as an alternative to traditional Rankine cycles for increasing net plant efficie...

  13. A novel 3D Ag(I)-MOF: Surfactant-directed syntheses and catalytic degradation of o/m/p-Nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xue-Qian [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Wen, Guo-Xuan [College of Science, China Three Gorges University, Yichang 443002 (China); Wu, Ya-Pan; Dong, Wen-Wen; Zhao, Jun [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang 443002 (China)

    2016-10-15

    For the first time, sodium caprylate has been investigated to direct the crystal growth of 3D Ag-MOF, [Ag{sub 2}(ddcba)(4,4′-bipy){sub 2}] (1), constructing from 3,5-(di(2′,5′-dicarboxylphenyl)benozoic acid and 4,4′-bipy. The single crystal diffraction analyses shows that complex 1 possess 3D neutral framework with a three-connected ThSi{sub 2} (10{sup 3}-b) topology. Compound 1 exhibits predominant catalytic activity towards the degradation of o-Nitrophenol (ONP), m-Nitrophenol (MNP) and p-Nitrophenol (PNP) in aqueous solution. The kinetics of such catalytic degradation reactions was also studied. - Graphical abstract: A novel 3D Ag(I)-MOF with ThSi{sub 2} (10{sup 3}-b) topology exhibits predominant catalytic activity towards the degradation of o-Nitrophenol (ONP), m-Nitrophenol (MNP) and p-Nitrophenol (PNP) in aqueous solution. - Highlights: • A novel 3D Ag(I)-MOF with ThSi{sub 2} (10{sup 3}-b) topology. • Surfactant as additive for directing the crystal growth. • Predominant catalytic activities for the degradation of o/m/p-nitrophenol.

  14. Steam reformer with catalytic combustor

    Science.gov (United States)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  15. Mathematical interpretation of Brownian motor model: Limit cycles and directed transport phenomena

    Science.gov (United States)

    Yang, Jianqiang; Ma, Hong; Zhong, Suchuang

    2018-03-01

    In this article, we first suggest that the attractor of Brownian motor model is one of the reasons for the directed transport phenomenon of Brownian particle. We take the classical Smoluchowski-Feynman (SF) ratchet model as an example to investigate the relationship between limit cycles and directed transport phenomenon of the Brownian particle. We study the existence and variation rule of limit cycles of SF ratchet model at changing parameters through mathematical methods. The influences of these parameters on the directed transport phenomenon of a Brownian particle are then analyzed through numerical simulations. Reasonable mathematical explanations for the directed transport phenomenon of Brownian particle in SF ratchet model are also formulated on the basis of the existence and variation rule of the limit cycles and numerical simulations. These mathematical explanations provide a theoretical basis for applying these theories in physics, biology, chemistry, and engineering.

  16. Dissecting the Catalytic Mechanism of Betaine-Homocysteine S-Methyltransferase Using Intrinsic Tryptophan Fluorescence and Site-Directed Mutagenesis

    Energy Technology Data Exchange (ETDEWEB)

    Castro, C.; Gratson, A.A.; Evans, J.C.; Jiracek, J.; Collinsova, M.; Ludwig, M.L.; Garrow, T.A. (ASCR); (UIUC); (Michigan)

    2010-03-05

    Betaine-homocysteine S-methyltransferase (BHMT) is a zinc-dependent enzyme that catalyzes the transfer of a methyl group from glycine betaine (Bet) to homocysteine (Hcy) to form dimethylglycine (DMG) and methionine (Met). Previous studies in other laboratories have indicated that catalysis proceeds through the formation of a ternary complex, with a transition state mimicked by the inhibitor S-({delta}-carboxybutyl)-l-homocysteine (CBHcy). Using changes in intrinsic tryptophan fluorescence to determine the affinity of human BHMT for substrates, products, or CBHcy, we now demonstrate that the enzyme-substrate complex reaches its transition state through an ordered bi-bi mechanism in which Hcy is the first substrate to bind and Met is the last product released. Hcy, Met, and CBHcy bind to the enzyme to form binary complexes with K{sub d} values of 7.9, 6.9, and 0.28 {micro}M, respectively. Binary complexes with Bet and DMG cannot be detected with fluorescence as a probe, but Bet and DMG bind tightly to BHMT-Hcy to form ternary complexes with K{sub d} values of 1.1 and 0.73 {micro}M, respectively. Mutation of each of the seven tryptophan residues in human BHMT provides evidence that the enzyme undergoes two distinct conformational changes that are reflected in the fluorescence of the enzyme. The first is induced when Hcy binds, and the second, when Bet binds. As predicted by the crystal structure of BHMT, the amino acids Trp44 and Tyr160 are involved in binding Bet, and Glu159 in binding Hcy. Replacing these residues by site-directed mutagenesis significantly reduces the catalytic efficiency (V{sub max}/K{sub m}) of the enzyme. Replacing Tyr77 with Phe abolishes enzyme activity.

  17. Evaluation of technical feasibility of closed-cycle non-equilibrium MHD power generation with direct coal firing. Final report, Task 1

    Energy Technology Data Exchange (ETDEWEB)

    1981-11-01

    Program accomplishments in a continuing effort to demonstrate the feasibility of direct coal fired, closed cycle, magnetohydrodynamic power generation are detailed. These accomplishments relate to all system aspects of a CCMHD power generation system including coal combustion, heat transfer to the MHD working fluid, MHD power generation, heat and cesium seed recovery and overall systems analysis. Direct coal firing of the combined cycle has been under laboratory development in the form of a high slag rejection, regeneratively air cooled cyclone coal combustor concept, originated within this program. A hot bottom ceramic regenerative heat exchanger system was assembled and test fired with coal for the purposes of evaluating the catalytic effect of alumina on NO/sub x/ emission reduction and operability of the refractory dome support system. Design, procurement, fabrication and partial installation of a heat and seed recovery flow apparatus was accomplished and was based on a stream tube model of the full scale system using full scale temperatures, tube sizes, rates of temperature change and tube geometry. Systems analysis capability was substantially upgraded by the incorporation of a revised systems code, with emphasis on ease of operator interaction as well as separability of component subroutines. The updated code was used in the development of a new plant configuration, the Feedwater Cooled (FCB) Brayton Cycle, which is superior to the CCMHD/Steam cycle both in performance and cost. (WHK)

  18. Influence of boron concentration on growth characteristic and electro-catalytic performance of boron-doped diamond electrodes prepared by direct current plasma chemical vapor deposition

    International Nuclear Information System (INIS)

    Feng Yujie; Lv Jiangwei; Liu Junfeng; Gao Na; Peng Hongyan; Chen Yuqiang

    2011-01-01

    A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH 4 /H 2 /B(OCH 3 ) 3 gas mixture. A maximum growth rate of 0.65 mg cm -2 h -1 was obtained with CH 4 /H 2 /B(OCH 3 ) 3 radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH 3 ) 3 that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 10 20 cm -3 with CH 4 /H 2 /B(OCH 3 ) 3 ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH 4 /H 2 /B(OCH 3 ) 3 ratio of 4/190/10 possessed the best phenol removal efficiency.

  19. A study about the contribution of the α-β phase transition of quartz to thermal cycle damage of a refractory used in fluidized catalytic cracking units

    Directory of Open Access Journals (Sweden)

    A. H. A. Pereira

    2014-09-01

    Full Text Available The deterioration of refractories used in fluidized catalytic cracking units (FCC-units is responsible for high costs of maintenance for the petrochemical industry. This is commonly associated with coke deposition during the production of light hydrocarbons. However, other mechanisms responsible for causing damage may also occur, such as the generation of cracks by expansive phase transition. The aim of the work herein was to study the contribution of the a-b phase transition of quartz particles to the deterioration of a commercial aluminosilicate refractory used in a riser by the means of slow thermal cycles. Such damage may occur if the working temperature of the equipment fluctuates around the a-b transition temperature (573 °C. The current study considered the material with and without coke impregnation to evaluate the combined effect of coke presence and phase transition. To evaluate the damage, it was used the Young's modulus as a function of temperature by applying the Impulse Excitation Technique under controlled atmosphere. An equipment recently developed by the authors research group was applied. Specimens were prepared and submitted to slow thermal cycles of temperatures up to 500 °C and up to 700 °C, with a heating rate of 2 °C/min. Part of the specimens was previously impregnated with coke by a reactor using propen. To complete the evaluation, characterization by X-ray diffraction, as well as by dilatometry and scanning electron microscopy were performed. The findings of this study showed that the presence of quartz particles determine the thermo-mechanical behaviour of the material, as well as the thermocycling damage resistance. In spite of the fact that the a-b phase transition stiffens the material during the heating stage, it increases the damage by slow thermal cycling. The coke impregnation increases the resistance to slow thermal cycles, however it decreases the resistance to the damage evolution.

  20. Sinusoidal potential cycling operation of a direct ethanol fuel cell to improving carbon dioxide yields

    Science.gov (United States)

    Majidi, Pasha; Pickup, Peter G.

    2014-12-01

    A direct ethanol fuel cell has been operated under sinusoidal (AC) potential cycling conditions in order to increase the yield of carbon dioxide and thereby increase cell efficiency relative to operation at a fixed potential. At 80 °C, faradaic yields of CO2 as high as 25% have been achieved with a PtRu anode catalyst, while the maximum CO2 production at constant potential was 13%. The increased yields under cycling conditions have been attributed to periodic oxidative stripping of adsorbed CO. These results will be important in the optimization of operating conditions for direct ethanol fuel cells, where the benefits of potential cycling are projected to increase as catalysts that produce CO2 more efficiently are implemented.

  1. Electric power generating plant having direct-coupled steam and compressed-air cycles

    Science.gov (United States)

    Drost, M.K.

    1981-01-07

    An electric power generating plant is provided with a Compressed Air Energy Storage (CAES) system which is directly coupled to the steam cycle of the generating plant. The CAES system is charged by the steam boiler during off peak hours, and drives a separate generator during peak load hours. The steam boiler load is thereby levelized throughout an operating day.

  2. Electric power generating plant having direct coupled steam and compressed air cycles

    Science.gov (United States)

    Drost, Monte K.

    1982-01-01

    An electric power generating plant is provided with a Compressed Air Energy Storage (CAES) system which is directly coupled to the steam cycle of the generating plant. The CAES system is charged by the steam boiler during off peak hours, and drives a separate generator during peak load hours. The steam boiler load is thereby levelized throughout an operating day.

  3. Tree-type values for cycle-free directed graph games

    NARCIS (Netherlands)

    Khmelnitskaya, Anna Borisovna; Talman, Dolf

    2010-01-01

    For arbitrary cycle-free directed graph games tree-type values are introduced axiomatically and their explicit formula representation is provided. These values may be considered as natural extensions of the tree and sink values as has been defined correspondingly for rooted and sink forest graph

  4. Man o' War Mutation in UDP-α-D-Xylose Synthase Favors the Abortive Catalytic Cycle and Uncovers a Latent Potential for Hexamer Formation

    Energy Technology Data Exchange (ETDEWEB)

    Walsh, Jr., Richard M.; Polizzi, Samuel J.; Kadirvelraj, Renuka; Howard, Wesley W.; Wood, Zachary A. [Georgia

    2015-03-17

    The man o’ war (mow) phenotype in zebrafish is characterized by severe craniofacial defects due to a missense mutation in UDP-α-D-xylose synthase (UXS), an essential enzyme in proteoglycan biosynthesis. The mow mutation is located in the UXS dimer interface ~16 Å away from the active site, suggesting an indirect effect on the enzyme mechanism. We have examined the structural and catalytic consequences of the mow mutation (R236H) in the soluble fragment of human UXS (hUXS), which shares 93% sequence identity with the zebrafish enzyme. In solution, hUXS dimers undergo a concentration-dependent association to form a tetramer. Sedimentation velocity studies show that the R236H substitution induces the formation of a new hexameric species. Using two new crystal structures of the hexamer, we show that R236H and R236A substitutions cause a local unfolding of the active site that allows for a rotation of the dimer interface necessary to form the hexamer. The disordered active sites in the R236H and R236A mutant constructs displace Y231, the essential acid/base catalyst in the UXS reaction mechanism. The loss of Y231 favors an abortive catalytic cycle in which the reaction intermediate, UDP-α-D-4-keto-xylose, is not reduced to the final product, UDP-α-D-xylose. Surprisingly, the mow-induced hexamer is almost identical to the hexamers formed by the deeply divergent UXS homologues from Staphylococcus aureus and Helicobacter pylori (21% and 16% sequence identity, respectively). The persistence of a latent hexamer-building interface in the human enzyme suggests that the ancestral UXS may have been a hexamer.

  5. H/D exchange mass spectrometry and statistical coupling analysis reveal a role for allostery in a ferredoxin-dependent bifurcating transhydrogenase catalytic cycle.

    Science.gov (United States)

    Berry, Luke; Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R; Nguyen, Diep M N; Schut, Gerrit J; Adams, Michael W W; Peters, John W; Boyd, Eric S; Bothner, Brian

    2018-01-01

    Recent investigations into ferredoxin-dependent transhydrogenases, a class of enzymes responsible for electron transport, have highlighted the biological importance of flavin-based electron bifurcation (FBEB). FBEB generates biomolecules with very low reduction potential by coupling the oxidation of an electron donor with intermediate potential to the reduction of high and low potential molecules. Bifurcating systems can generate biomolecules with very low reduction potentials, such as reduced ferredoxin (Fd), from species such as NADPH. Metabolic systems that use bifurcation are more efficient and confer a competitive advantage for the organisms that harbor them. Structural models are now available for two NADH-dependent ferredoxin-NADP + oxidoreductase (Nfn) complexes. These models, together with spectroscopic studies, have provided considerable insight into the catalytic process of FBEB. However, much about the mechanism and regulation of these multi-subunit proteins remains unclear. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS) and statistical coupling analysis (SCA), we identified specific pathways of communication within the model FBEB system, Nfn from Pyrococus furiosus, under conditions at each step of the catalytic cycle. HDX-MS revealed evidence for allosteric coupling across protein subunits upon nucleotide and ferredoxin binding. SCA uncovered a network of co-evolving residues that can provide connectivity across the complex. Together, the HDX-MS and SCA data show that protein allostery occurs across the ensemble of iron‑sulfur cofactors and ligand binding sites using specific pathways that connect domains allowing them to function as dynamically coordinated units. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Study on the reactive transient α-λ3-iodanyl-acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed α-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Wang, Hao-Yang; Zhou, Juan; Guo, Yin-Long

    2012-03-30

    Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed α-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive α-λ(3)-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the transient reactive α-λ(3)-iodine alkyl acetophenone intermediate in the reaction solution. The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3·H(+) was observed at m/z 383 from the reaction solution and this ion gave the protonated α-acetoxylation product 4·H(+) at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. These ESI-MS/MS studies showed the existence of the reactive α-λ(3)-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H(+) was consistent with the proposed solution-phase reactivity of the α-λ(3)-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright © 2012 John Wiley & Sons, Ltd.

  7. Non-catalytic direct synthesis of graphene on Si (111) wafers by using inductively-coupled plasma chemical vapor deposition

    Science.gov (United States)

    Hwang, Sung Won; Shin, Hyunho; Lee, Bongsoo; Choi, Suk-Ho

    2016-08-01

    We employ inductively-coupled plasma chemical vapor deposition for non-catalytic growth of graphene on a Si (111) wafer or glass substrate, which is useful for practical device applications of graphene without transfer processes. At a RF power (P) of 500 W under C2H2 flow, defect-free 3 ˜ 5-layer graphene is grown on Si (111) wafers, but on glass substrate, the layer is thicker and defective, as characterized by Raman spectroscopy and electron microscopy. The graphene is produced on Si (111) for P down to 190 W whereas it is almost not formed on glass for P < 250 W, possibly resulting from the weak catalytic-reaction-like effect on glass. These results are discussed based on possible growth mechanisms.

  8. Life cycle assessment of selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator

    DEFF Research Database (Denmark)

    Møller, Jacob; Munk, Bjarne; Crillesen, Kim

    2011-01-01

    Selective non-catalytic reduction (SNCR) of nitrous oxides in a full-scale municipal solid waste incinerator was investigated using LCA. The relationship between NOx-cleaning and ammonia dosage was measured at the plant. Un-reacted ammonia – the ammonia slip – leaving the flue-gas cleaning system......-cleaning efficiency, the fate of the ammonia slip as well as the environmental impact from ammonia production, the potential acidification and nutrient enrichment from NOx-cleaning was calculated as a function of ammonia dosage. Since the exact fate of the ammonia slip could not be measured directly, a number...... of scenarios were set up ranging from “best case” with no ammonia from the slip ending up in the environment to “worst case” where all the ammonia slip eventually ended up in the environment and contributed to environmental pollution. In the “best case” scenario the highest ammonia dosage was most beneficial...

  9. Thermodynamically accurate modeling of the catalytic cycle of photosynthetic oxygen evolution: a mathematical solution to asymmetric Markov chains.

    Science.gov (United States)

    Vinyard, David J; Zachary, Chase E; Ananyev, Gennady; Dismukes, G Charles

    2013-07-01

    Forty-three years ago, Kok and coworkers introduced a phenomenological model describing period-four oscillations in O2 flash yields during photosynthetic water oxidation (WOC), which had been first reported by Joliot and coworkers. The original two-parameter Kok model was subsequently extended in its level of complexity to better simulate diverse data sets, including intact cells and isolated PSII-WOCs, but at the expense of introducing physically unrealistic assumptions necessary to enable numerical solutions. To date, analytical solutions have been found only for symmetric Kok models (inefficiencies are equally probable for all intermediates, called "S-states"). However, it is widely accepted that S-state reaction steps are not identical and some are not reversible (by thermodynamic restraints) thereby causing asymmetric cycles. We have developed a mathematically more rigorous foundation that eliminates unphysical assumptions known to be in conflict with experiments and adopts a new experimental constraint on solutions. This new algorithm termed STEAMM for S-state Transition Eigenvalues of Asymmetric Markov Models enables solutions to models having fewer adjustable parameters and uses automated fitting to experimental data sets, yielding higher accuracy and precision than the classic Kok or extended Kok models. This new tool provides a general mathematical framework for analyzing damped oscillations arising from any cycle period using any appropriate Markov model, regardless of symmetry. We illustrate applications of STEAMM that better describe the intrinsic inefficiencies for photon-to-charge conversion within PSII-WOCs that are responsible for damped period-four and period-two oscillations of flash O2 yields across diverse species, while using simpler Markov models free from unrealistic assumptions. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. CO{sub 2} direct cycles suitable for AGR type reactors; Cycles directs de gaz carbonique applicables aux reacteurs du genre AGR

    Energy Technology Data Exchange (ETDEWEB)

    Maillet, E [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)

    1967-10-01

    The perspectives given by the gas turbines under pressure, to build simple nuclear power plants and acieving significantly high yield, are specified. The CO{sub 2} is characterised by by good efficiency under moderate temperature (500 to 750 Celsius degrees), compactness and the simpleness of machines and the safe exploitation (supply, storage, relief cooling, thermosyphon). The revision of thermal properties of the CO{sub 2} and loss elements show that several direct cycles would fit in particular to the AGR type reactors. Cycles that would diverge a little from classical models and able to lead to power and heat generation can lead by simple means to the best results. Several satisfying solutions present for the starting up, the power regulation and the stopping. The nuclear power plant components and the functioning safety are equally considered in the present report. The conclusions stimulate the studies and realizations of carbon dioxide gas turbines in when approprite. [French] Les perspectives offertes par la turbine a gaz sous pression, pour construire des centrales nucleaires simples et de rendement progressivement eleve, se precisent actuellement. le CO{sub 2} se distingue par sa bonne efficacite a temperature moderee (500 a 750 degres celsius), la compacite et la simplicite des machines, et la surete qu'il apporte a l'exploitation ( approvisionnement, stockage, refroidissement de secours, thermosiphon). La revision des proprietes thermophysiques du CO{sub 2} et des elements de pertes montre que divers cycles directs conviendraient en particulier aux reacteurs agr ou derives. Des cycles s'ecartant peu des modeles classiques, et se pretant ulterieurement a la production simultanee d'electricite et de chaleur, peuvent conduire par des moyens simples aux meilleurs resultats d'ensemble. Plusieurs solutions satisfaisantes se presentent pour le demarrage, le reglage de la puissance et l'arret. Les composants de la centrale et la surete de fonctionnement sont

  11. Direct versus indirect effects of tropospheric humidity changes on the hydrologic cycle

    International Nuclear Information System (INIS)

    Sherwood, S C

    2010-01-01

    Abundant evidence indicates that tropospheric specific humidity increases in a warmer atmosphere, at rates roughly comparable to those at constant relative humidity. While the implications for the planetary energy budget and global warming are well recognized, it is the net atmospheric cooling (or surface heating) that controls the hydrologic cycle. Relative humidity influences this directly through gas-phase radiative transfer, and indirectly by affecting cloud cover (and its radiative effects) and convective heating. Simple calculations show that the two indirect impacts are larger than the direct impact by roughly one and two orders of magnitude respectively. Global or regional relative humidity changes could therefore have significant indirect impacts on energy and water cycles, especially by altering deep convection, even if they are too small to significantly affect global temperature. Studies of climate change should place greater emphasis on these indirect links, which may not be adequately represented in models.

  12. Finding shortest non-trivial cycles in directed graphs on surfaces

    Directory of Open Access Journals (Sweden)

    Sergio Cabello

    2016-04-01

    Full Text Available Let $D$ be a weighted directed graph cellularly embedded in a surface of genus $g$, orientable or not, possibly with boundary.  We describe algorithms to compute shortest non-contractible and shortest surface non-separating cycles in $D$, generalizing previous results that dealt with undirected graphs.Our first algorithm computes such cycles in $O(n^2\\log n$ time, where $n$ is the total number of vertices and edges of $D$, thus matching the complexity of the best general algorithm in the undirected case.  It revisits and extends Thomassen's 3-path condition; the technique applies to other families of cycles as well.We also provide more efficient algorithms in special cases, such as graphs with small genus or bounded treewidth, using a divide-and-conquer technique that simplifies the graph while preserving the topological properties of its cycles.  Finally, we give an efficient output-sensitive algorithm, whose running time depends on the length of the shortest non-contractible or non-separating cycle.

  13. Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu

    2005-09-05

    The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

  14. Directly observing catalytic intermediates of methane dry reforming (MDR) on model Ni(111) catalyst via in operando surface techniques

    Science.gov (United States)

    Yuan, Kaidi

    In this work, near ambient pressure x-ray photoelectron spectroscopy was used to trace the in operando catalytic intermediates of methane dry reforming on model Ni(111) catalyst. The following reactive carbon intermediates have been characterized from dissociation of CH4: *CH, *C1 (Ni3C), *Cn (n≥2) and clock-reconstructed Ni2C. They can develop into inert graphene, and the conditions for this transition have been explored. One the other hand, the oxygen intermediates from CO2 dissociation were also studied, which play an important role on restraining graphene growth. Their dynamic coverage decreases with increasing temperature, which is suggested the fundamental mechanism of regional carbon overspill and causes irreversible graphene formation. Therefore, solutions based on Ni-O stabilization were proposed in developing coking resisting catalysts.

  15. Catalytic soman scavenging by Y337A/F338A acetylcholinesterase mutant assisted with novel site-directed aldoximes

    Science.gov (United States)

    Kovarik, Zrinka; Hrvat, Nikolina Maček; Katalinić, Maja; Sit, Rakesh K.; Paradyse, Alexander; Žunec, Suzana; Musilek, Kamil; Fokin, Valery V.; Taylor, Palmer; Radić, Zoran

    2016-01-01

    Exposure to the nerve agent soman is difficult to treat due to the rapid dealkylation of soman-acetylcholinesterase (AChE) conjugate known as aging. Oxime antidotes commonly used to reactivate organophosphate inhibited AChE are ineffective against soman, while the efficacy of the recommended nerve agent bioscavenger butyrylcholinesterase is limited by strictly stoichiometric scavenging. To overcome this limitation, we tested ex vivo, in human blood, and in vivo, in soman exposed mice, the capacity of aging-resistant human AChE mutant Y337A/F338A in combination with oxime HI-6 to act as a catalytic bioscavenger of soman. HI-6 was previously shown in vitro to efficiently reactivate this mutant upon soman, as well as VX, cyclosarin, sarin and paraoxon inhibition. We here demonstrate that ex vivo, in whole human blood, 1 μM soman was detoxified within 30 minutes when supplemented with 0.5 μM Y337A/F338A AChE and 100 μM HI-6. This combination was further tested in vivo. Catalytic scavenging of soman in mice improved the therapeutic outcome and resulted in the delayed onset of toxicity symptoms. Furthermore, in a preliminary in vitro screen we identified an even more efficacious oxime than HI-6, in a series of forty-two pyridinium aldoximes, and five imidazole 2-aldoxime N-propyl pyridinium derivatives. One of the later imidazole aldoximes, RS-170B, was a 2–3 –fold more effective reactivator of Y337A/F338A AChE than HI-6 due to the smaller imidazole ring, as indicated by computational molecular models, that affords a more productive angle of nucleophilic attack. PMID:25835984

  16. The Direct Internal Recycling concept to simplify the fuel cycle of a fusion power plant

    International Nuclear Information System (INIS)

    Day, Christian; Giegerich, Thomas

    2013-01-01

    Highlights: • The fusion fuel cycle is presented and its functions are discussed. • Tritium inventories are estimated for an early DEMO configuration. • The Direct Internal Recycling concept to reduce tritium inventories is described. • Concepts for its technical implementation are developed. -- Abstract: A new concept, the Direct Internal Recycling (DIR) concept, is proposed, which minimizes fuel cycle inventory by adding an additional short-cut between the pumped torus exhaust gas and the fuelling systems. The paper highlights quantitative modelling results derived from a simple fuel cycle spreadsheet which underline the potential benefits that can be achieved by implementation of the DIR concept into a fusion power plant. DIR requires a novel set-up of the torus exhaust pumping system, which replaces the batch-wise and cyclic operated cryogenic pumps by a continuous pumping solution and which offers at the same time an additional integral gas separation function. By that, hydrogen can be removed close to the divertor from all other gases and the main load to the fuel clean-up systems is a smaller, helium-rich gas stream. Candidate DIR relevant pump technology based on liquid metals (vapour diffusion and liquid ring pumps) and metal foils is discussed

  17. Cycle-Based Cluster Variational Method for Direct and Inverse Inference

    Science.gov (United States)

    Furtlehner, Cyril; Decelle, Aurélien

    2016-08-01

    Large scale inference problems of practical interest can often be addressed with help of Markov random fields. This requires to solve in principle two related problems: the first one is to find offline the parameters of the MRF from empirical data (inverse problem); the second one (direct problem) is to set up the inference algorithm to make it as precise, robust and efficient as possible. In this work we address both the direct and inverse problem with mean-field methods of statistical physics, going beyond the Bethe approximation and associated belief propagation algorithm. We elaborate on the idea that loop corrections to belief propagation can be dealt with in a systematic way on pairwise Markov random fields, by using the elements of a cycle basis to define regions in a generalized belief propagation setting. For the direct problem, the region graph is specified in such a way as to avoid feed-back loops as much as possible by selecting a minimal cycle basis. Following this line we are led to propose a two-level algorithm, where a belief propagation algorithm is run alternatively at the level of each cycle and at the inter-region level. Next we observe that the inverse problem can be addressed region by region independently, with one small inverse problem per region to be solved. It turns out that each elementary inverse problem on the loop geometry can be solved efficiently. In particular in the random Ising context we propose two complementary methods based respectively on fixed point equations and on a one-parameter log likelihood function minimization. Numerical experiments confirm the effectiveness of this approach both for the direct and inverse MRF inference. Heterogeneous problems of size up to 10^5 are addressed in a reasonable computational time, notably with better convergence properties than ordinary belief propagation.

  18. Directed modification of L-LcLDH1, an L-lactate dehydrogenase from Lactobacillus casei, to improve its specific activity and catalytic efficiency towards phenylpyruvic acid.

    Science.gov (United States)

    Li, Jian-Fang; Li, Xue-Qing; Liu, Yan; Yuan, Feng-Jiao; Zhang, Ting; Wu, Min-Chen; Zhang, Ji-Ru

    2018-05-22

    To improve the specific activity and catalytic efficiency of L-LcLDH1, an NADH-dependent allosteric L-lactate dehydrogenase from L. casei, towards phenylpyruvic acid (PPA), its directed modification was conducted based on the semi-rational design. The three variant genes, Lcldh1 Q88R , Lcldh1 I229A and Lcldh1 T235G , were constructed by whole-plasmid PCR as designed theoretically, and expressed in E. coli BL21(DE3), respectively. The purified mutant, L-LcLDH1 Q88R or L-LcLDH1 I229A , displayed the specific activity of 451.5 or 512.4 U/mg towards PPA, by which the asymmetric reduction of PPA afforded L-phenyllactic acid (PLA) with an enantiomeric excess (ee p ) more than 99%. Their catalytic efficiencies (k cat /K m ) without D-fructose-1,6-diphosphate (D-FDP) were 4.8- and 5.2-fold that of L-LcLDH1. Additionally, the k cat /K m values of L-LcLDH1 Q88R and L-LcLDH1 I229A with D-FDP were 168.4- and 8.5-fold higher than those of the same enzymes without D-FDP, respectively. The analysis of catalytic mechanisms by molecular docking (MD) simulation indicated that substituting I229 in L-LcLDH1 with Ala enlarges the space of substrate-binding pocket, and that the replacement of Q88 with Arg makes the inlet of pocket larger than that of L-LcLDH1. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Enhancement in catalytic activity of Aspergillus niger XynB by selective site-directed mutagenesis of active site amino acids.

    Science.gov (United States)

    Wu, Xiuyun; Tian, Zhennan; Jiang, Xukai; Zhang, Qun; Wang, Lushan

    2018-01-01

    XynB from Aspergillus niger ATCC1015 (AnXynB) is a mesophilic glycoside hydrolase (GH) family 11 xylanase which holds great potentials in a wide variety of industrial applications. In the present study, the catalytic activity and stability of AnXynB were improved by a combination of computational and experimental approaches. Virtual mutation and molecular dynamics simulations indicated that the introduction of Glu and Asn altered the interaction network at the - 3 subsite. Interestingly, the double mutant S41N/T43E displayed 72% increase in catalytic activity when compared to the wild type (WT). In addition, it also showed a better thermostability than the WT enzyme. Kinetic determination of the T43E and S41N/T43E mutants suggested that the higher xylanase activity is probably due to the increasing binding affinity of enzyme and substrate. Consequently, the enzyme activity and thermostability of AnXynB was both increased by selective site-directed mutagenesis at the - 3 subsite of its active site architecture which provides a good example for a successfully engineered enzyme for potential industrial application. Moreover, the molecular evolution approach adopted in this study led to the design of a library of sequences that captures a meaningful functional diversity in a limited number of protein variants.

  20. Enhancement of the catalytic activity of ferulic acid decarboxylase from Enterobacter sp. Px6-4 through random and site-directed mutagenesis.

    Science.gov (United States)

    Lee, Hyunji; Park, Jiyoung; Jung, Chaewon; Han, Dongfei; Seo, Jiyoung; Ahn, Joong-Hoon; Chong, Youhoon; Hur, Hor-Gil

    2015-11-01

    The enzyme ferulic acid decarboxylase (FADase) from Enterobacter sp. Px6-4 catalyzes the decarboxylation reaction of lignin monomers and phenolic compounds such as p-coumaric acid, caffeic acid, and ferulic acid into their corresponding 4-vinyl derivatives, that is, 4-vinylphenol, 4-vinylcatechol, and 4-vinylguaiacol, respectively. Among various ferulic acid decarboxylase enzymes, we chose the FADase from Enterobacter sp. Px6-4, whose crystal structure is known, and produced mutants to enhance its catalytic activity by random and site-directed mutagenesis. After three rounds of sequential mutations, FADase(F95L/D112N/V151I) showed approximately 34-fold higher catalytic activity than wild-type for the production of 4-vinylguaiacol from ferulic acid. Docking analyses suggested that the increased activity of FADase(F95L/D112N/V151I) could be due to formation of compact active site compared with that of the wild-type FADase. Considering the amount of phenolic compounds such as lignin monomers in the biomass components, successfully bioengineered FADase(F95L/D112N/V151I) from Enterobacter sp. Px6-4 could provide an ecofriendly biocatalytic tool for producing diverse styrene derivatives from biomass.

  1. Surface Reduced CeO2 Nanowires for Direct Conversion of CO2 and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy

    Directory of Open Access Journals (Sweden)

    Zhongwei Fu

    2018-04-01

    Full Text Available Ultralong 1D CeO2 nanowires were synthesized via an advanced solvothermal method, surface reduced under H2 atmosphere, and first applied in direct synthesis of dimethyl carbonate (DMC from CO2 and CH3OH. The micro morphologies, physical parameters of nanowires were fully investigated by transmission electron microscopy (TEM, X-ray diffraction (XRD, N2 adsorption, X-ray photoelectron spectrum (XPS, and temperature-programmed desorption of ammonia/carbon dioxide (NH3-TPD/CO2-TPD. The effects of surface oxygen vacancy and acidic/alkaline sites on the catalytic activity was explored. After reduction, the acidic/alkaline sites of CeO2 nanowires can be dramatically improved and evidently raised the catalytic performance. CeO2 nanowires reduced at 500 °C (CeO2_NW_500 exhibited notably superior activity with DMC yield of 16.85 mmol gcat−1. Furthermore, kinetic insights of initial rate were carried out and the apparent activation energy barrier of CeO2_NW_500 catalyst was found to be 41.9 kJ/mol, much tiny than that of CeO2_NW catalyst (74.7 KJ/mol.

  2. Experimental and modeling study of high performance direct carbon solid oxide fuel cell with in situ catalytic steam-carbon gasification reaction

    Science.gov (United States)

    Xu, Haoran; Chen, Bin; Zhang, Houcheng; Tan, Peng; Yang, Guangming; Irvine, John T. S.; Ni, Meng

    2018-04-01

    In this paper, 2D models for direct carbon solid oxide fuel cells (DC-SOFCs) with in situ catalytic steam-carbon gasification reaction are developed. The simulation results are found to be in good agreement with experimental data. The performance of DC-SOFCs with and without catalyst are compared at different operating potential, anode inlet gas flow rate and operating temperature. It is found that adding suitable catalyst can significantly speed up the in situ steam-carbon gasification reaction and improve the performance of DC-SOFC with H2O as gasification agent. The potential of syngas and electricity co-generation from the fuel cell is also evaluated, where the composition of H2 and CO in syngas can be adjusted by controlling the anode inlet gas flow rate. In addition, the performance DC-SOFCs and the percentage of fuel in the outlet gas are both increased with increasing operating temperature. At a reduced temperature (below 800 °C), good performance of DC-SOFC can still be obtained with in-situ catalytic carbon gasification by steam. The results of this study form a solid foundation to understand the important effect of catalyst and related operating conditions on H2O-assisted DC-SOFCs.

  3. Direct photoaffinity labeling by nucleotides of the apparent catalytic site on the heavy chains of smooth muscle and Acanthamoeba myosins

    International Nuclear Information System (INIS)

    Maruta, H.; Korn, E.D.

    1981-01-01

    The heavy chains of Acanthamoeba myosins, IA, IB and II, turkey gizzard myosin, and rabbit skeletal muscle myosin subfragment-1 were specifically labeled by radioactive ATP, ADP, and UTP, each of which is a substrate or product of myosin ATPase activity, when irradiated with uv light at 0 0 C. With UTP, as much as 0.45 mol/mol of Acanthamoeba myosin IA heavy chain and 1 mol/mol of turkey gizzard myosin heavy chain was incorporated. Evidence that the ligands were associated with the catalytic site included the observations that reaction occurred only with nucleotides that are substrates or products of the ATPase activity; that the reaction was blocked by pyrophosphate which is an inhibitor of the ATPase activity; that ATP was bound as ADP; and that label was probably restricted to a single peptide following limited subtilisin proteolysis of labeled Acanthamoeba myosin IA heavy chain and extensive cleavage with CNBr and trypsin of labeled turkey gizzard myosin heavy chain

  4. Bearing compartment seal systems for turbomachinery in direct-cycle HTGR power plants

    International Nuclear Information System (INIS)

    Adams, R.G.; Boenig, F.H.; Pfeifer, G.D.

    1977-10-01

    The direct-cycle High-Temperature Gas-Cooled Reactor (HTGR) employs a closed gas-turbine cycle with the primary reactor coolant (helium) as the working fluid. Design studies on this type of plant, carried out since 1971, have demonstrated, among other points, the advantages of the integrated arrangement, in which power from the cycle is transmitted to the electric generators by turbomachines completely enclosed in the reactor pressure vessel. A result of this arrangement is that the bearings are entirely enclosed within the primary coolant system of the reactor. An important aspect of the design of the turbomachinery is its prevention or minimization of the ingress of lubricants into the primary coolant system and its prevention of ingress of primary coolant into the bearing compartments. The design studies, which included thorough conceptual designs of the turbomachinery with emphasis on bearings and seals and their support systems showed that total exclusion of lubricant requires extremely complex seals and seal support systems. The variation of system low-end pressure with control actuation and the requirement that the bearing cavity pressure follow these variations were proved to further complicate the service system. The tolerance of even relatively minute amounts of entering lubricant during control transients will allow considerable simplification. This paper discusses the above-mentioned problems and their solutions in tracing the design evolution of a satisfactory bearing-compartment seals and service system. The resulting system appears to be feasible on the basis of experience with industrial gas turbines

  5. Prospects of power conversion technology of direct-cycle helium gas turbine for MHTGR

    International Nuclear Information System (INIS)

    Li Yong; Zhang Zuoyi

    1999-01-01

    The modular high temperature gas cooled reactor (MHTGR) is a modern passively safe reactor. The reactor and helium gas turbine may be combined for high efficiency's power conversion, because MHTGR has high outlet temperature up to 950 degree C. Two different schemes are planed separately by USA and South Africa. the helium gas turbine methodologies adopted by them are mainly based on the developed heavy duty industrial and aviation gas turbine technology. The author introduces the differences of two technologies and some design issues in the design and manufacture. Moreover, the author conclude that directly coupling a closed Brayton cycle gas turbine concept to the passively safe MHTGR is the developing direction of MHTGR due to its efficiency which is much higher than that of using steam turbine

  6. Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study

    Science.gov (United States)

    Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J.; Martínez, Angel T.

    2014-01-01

    Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H2O2-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (kcat> 200 s−1) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 kcat ~20 s−1) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant. PMID:25495127

  7. Performance analysis of an Integrated Solar Combined Cycle using Direct Steam Generation in parabolic trough collectors

    International Nuclear Information System (INIS)

    Montes, M.J.; Rovira, A.; Munoz, M.; Martinez-Val, J.M.

    2011-01-01

    Highlights: → Solar hybridization improves the performance of CCGT in a very hot and dry weather. → The scheme analyzed is a DSG parabolic trough field coupled to the Rankine cycle. → An annual simulation has been carried out for two locations: Almeria and Las Vegas. → Economical analysis shows that this scheme is a cheaper way to exploit solar energy. → For that, solar hybridization must be limited to a small fraction of the CCGT power. - Abstract: The contribution of solar thermal power to improve the performance of gas-fired combined cycles in very hot and dry environmental conditions is analyzed in this work, in order to assess the potential of this technique, and to feature Direct Steam Generation (DSG) as a well suited candidate for achieving very good results in this quest. The particular Integrated Solar Combined Cycle (ISCC) power plant proposed consists of a DSG parabolic trough field coupled to the bottoming steam cycle of a Combined Cycle Gas Turbine (CCGT) power plant. For this analysis, the solar thermal power plant performs in a solar dispatching mode: the gas turbine always operates at full load, only depending on ambient conditions, whereas the steam turbine is somewhat boosted to accommodate the thermal hybridization from the solar field. Although the analysis is aimed to studying such complementary effects in the widest perspective, two relevant examples are given, corresponding to two well-known sites: Almeria (Spain), with a mediterranean climate, and Las Vegas (USA), with a hot and dry climate. The annual simulations show that, although the conventional CCGT power plant works worse in Las Vegas, owing to the higher temperatures, the ISCC system operates better in Las Vegas than in Almeria, because of solar hybridization is especially well coupled to the CCGT power plant in the frequent days with great solar radiation and high temperatures in Las Vegas. The complementary effect will be clearly seen in these cases, because the thermal

  8. Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4+2] Annulation.

    Science.gov (United States)

    Chiou, Mong-Feng; Jayakumar, Jayachandran; Cheng, Chien-Hong; Chuang, Shih-Ching

    2018-06-13

    Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M I /M III , M = Co and Rh) generally favor a [3+2] cyclization pathway, whereas those involving higher oxidation states (M III /M V ) proceed through a [4+2] cyclization pathway. A catalytic cycle with novel M III /M V as a crucial species was successfully revealed for isoquinolinium salts synthesis, which highly valent M V was not only encountered in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

  9. Studies of Catalytic Model Systems

    DEFF Research Database (Denmark)

    Holse, Christian

    The overall topic of this thesis is within the field of catalysis, were model systems of different complexity have been studied utilizing a multipurpose Ultra High Vacuum chamber (UHV). The thesis falls in two different parts. First a simple model system in the form of a ruthenium single crystal...... of the Cu/ZnO nanoparticles is highly relevant to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boost the catalytic activity. The dynamical behavior of the nanoparticles under reducing and oxidizing environments were studied by means of ex situ X......-ray Photoelectron Electron Spectroscopy (XPS) and in situ Transmission Electron Microscopy (TEM). The surface composition of the nanoparticles changes reversibly as the nanoparticles exposed to cycles of high-pressure oxidation and reduction (200 mbar). Furthermore, the presence of metallic Zn is observed by XPS...

  10. Plant accident dynamics of high-temperature reactors with direct gas turbine cycle

    International Nuclear Information System (INIS)

    Waloch, M.L.

    1977-01-01

    In the paper submitted, a one-dimensional accident simulation model for high-temperature reactors with direct-cycle gas turbine (single-cycle facilities) is described. The paper assesses the sudden failure of a gas duct caused by the double-ended break of one out of several parallel pipes before and behind the reactor for a non-integrated plant, leading to major loads in the reactor region, as well as the complete loss of vanes of the compressor for an integrated plant. The results of the calculations show especially high loads for the break of a hot-gas pipe immediately behind the flow restrictors of the reactor outlet, because of prolonged effects of pressure gradients in the reactor region and the maximum core differential pressure. A plant accident dynamics calculation therefore allows to find a compromise between the requirements of stable compressor operation, on the one hand, and small loads in the reactor in the course of an accident, on the other, by establishing in a co-ordinated manner the narrowing ratio of the flow restrictors. (GL) [de

  11. Organic Rankine cycle – review and research directions in engine applications

    Directory of Open Access Journals (Sweden)

    Panesar Angad

    2017-01-01

    Full Text Available Waste heat to power conversion using Organic Rankine Cycles (ORC is expected to play an important role in CO2 reductions from diesel engines. Firstly, a review of automotive ORCs is presented focusing on the pure working fluids, thermal architectures and expanders. The discussion includes, but is not limited to: R245fa, ethanol and water as fluids; series, parallel and cascade as architectures; dry saturated, superheated and supercritical as expansion conditions; and scroll, radial turbine and piston as expansion machines. Secondly, research direction in versatile expander and holistic architecture (NOx + CO2 are proposed. Benefits of using the proposed unconventional approaches are quantified using Ricardo Wave and Aspen HYSYS for diesel engine and ORC modelling. Results indicate that, the implementation of versatile piston expander tolerant to two-phase and using cyclopentane can potentially increase the highway drive cycle power by 8%. Furthermore, holistic architecture offering complete utilisation of charge air and exhaust recirculation heat increased the performance noticeably to 5% of engine power at the design point condition.

  12. Analysis of a BWR direct cycle forced circulation power plants operation

    International Nuclear Information System (INIS)

    Andrade, G.G. de.

    1973-01-01

    First, it is established a general view over the operational problems of the BWR direct cycle forced circulation power plants, and then it is analysed the possibility of the utilization of the energy purged from the turbine as an additional energy for the electrical generation. To simulate the BWR power plant and to obtain the solution of the mathematical model it was developed a computer code named ATOR which shows the feasibility of the proposed method. In this way it is shown the possibility to get a better maneuvering allowance for the BWR power plant whenever it is permitted a convenient use of the vapor extracted from the turbine for the feedwater pre-heaters of the reactor. (author)

  13. Influence of observed diurnal cycles of aerosol optical depth on aerosol direct radiative effect

    Directory of Open Access Journals (Sweden)

    A. Arola

    2013-08-01

    Full Text Available The diurnal variability of aerosol optical depth (AOD can be significant, depending on location and dominant aerosol type. However, these diurnal cycles have rarely been taken into account in measurement-based estimates of aerosol direct radiative forcing (ADRF or aerosol direct radiative effect (ADRE. The objective of our study was to estimate the influence of diurnal aerosol variability at the top of the atmosphere ADRE estimates. By including all the possible AERONET sites, we wanted to assess the influence on global ADRE estimates. While focusing also in more detail on some selected sites of strongest impact, our goal was to also see the possible impact regionally. We calculated ADRE with different assumptions about the daily AOD variability: taking the observed daily AOD cycle into account and assuming diurnally constant AOD. Moreover, we estimated the corresponding differences in ADREs, if the single AOD value for the daily mean was taken from the the Moderate Resolution Imaging Spectroradiometer (MODIS Terra or Aqua overpass times, instead of accounting for the true observed daily variability. The mean impact of diurnal AOD variability on 24 h ADRE estimates, averaged over all AERONET sites, was rather small and it was relatively small even for the cases when AOD was chosen to correspond to the Terra or Aqua overpass time. This was true on average over all AERONET sites, while clearly there can be much stronger impact in individual sites. Examples of some selected sites demonstrated that the strongest observed AOD variability (the strongest morning afternoon contrast does not typically result in a significant impact on 24 h ADRE. In those cases, the morning and afternoon AOD patterns are opposite and thus the impact on 24 h ADRE, when integrated over all solar zenith angles, is reduced. The most significant effect on daily ADRE was induced by AOD cycles with either maximum or minimum AOD close to local noon. In these cases, the impact on

  14. Mid-Term Direction of JAEA Nuclear Fuel Cycle Engineering Laboratories

    International Nuclear Information System (INIS)

    Ojima, H.; Sugiyama, T.; Tanaka, K.; Takeda, S.; Nomura, S.

    2009-01-01

    1. Introduction Nuclear Fuel Cycle Engineering Laboratories (NCL) of Japan Atomic Energy Agency (JAEA) has sufficient experience and ability through its 50 year operation to establish the next generation closed cycle. It strives to become a world-class Center Of Excellence. 2. Current activity in NCL: 1) - Recycling of MOX fuel: The Tokai Reprocessing Plant has reprocessed 29 tons of MOX fuel from the ATR Fugenh as a part of 1140 tons of cumulative spent fuel reprocessed. JAEA has supported the pre-operation of the Rokkasho Reprocessing Plant. An innovative MOX pellet fabrication process has been developed in the Plutonium Fuel Development Center, and a part of products obtained by the development are used as a fuel for core confirmation test for re-startup of the FBR Monjuh. Characterization of MOX containing Am and Np has been studied and a new data such as melting point and thermal conductivity were reported. In the Chemical Processing Facility, a hot lab., an advanced aqueous reprocessing technology has been tested for TRU recovery, economical improvement, etc., using irradiated MOX fuel from the FR Joyoh. 2) - Supporting Activity: JAEA has improved the effectiveness and efficiency of existing safeguards activities. The Integrated Safeguards approach for all facilities in NCL has been implemented since August, 2008, as a pioneer and a good example in the world. To reduce anxiety among local residents, NCL has explained its operation plans and exchanged information and opinions with them concerning potential risks to health and environment. Recently, stake-holder participation in the management of NCL was started from the view point of Corporate Social Responsibility. In April, 2008, the agreement was signed with Idaho National Laboratory for cooperation of personnel training in fuel cycle area. 3. Mid-Term Direction: In Japan, feasibility and direction of the transition period from the LWR era to the FBR era should be discussed for the next several years. Study

  15. Mid-Term Direction of JAEA Nuclear Fuel Cycle Engineering Laboratories

    Energy Technology Data Exchange (ETDEWEB)

    Ojima, H.; Sugiyama, T.; Tanaka, K.; Takeda, S.; Nomura, S. [Tokai-mura, Ibaraki-ken 319-1194 (Japan)

    2009-06-15

    1. Introduction Nuclear Fuel Cycle Engineering Laboratories (NCL) of Japan Atomic Energy Agency (JAEA) has sufficient experience and ability through its 50 year operation to establish the next generation closed cycle. It strives to become a world-class Center Of Excellence. 2. Current activity in NCL: 1) - Recycling of MOX fuel: The Tokai Reprocessing Plant has reprocessed 29 tons of MOX fuel from the ATR Fugenh as a part of 1140 tons of cumulative spent fuel reprocessed. JAEA has supported the pre-operation of the Rokkasho Reprocessing Plant. An innovative MOX pellet fabrication process has been developed in the Plutonium Fuel Development Center, and a part of products obtained by the development are used as a fuel for core confirmation test for re-startup of the FBR Monjuh. Characterization of MOX containing Am and Np has been studied and a new data such as melting point and thermal conductivity were reported. In the Chemical Processing Facility, a hot lab., an advanced aqueous reprocessing technology has been tested for TRU recovery, economical improvement, etc., using irradiated MOX fuel from the FR Joyoh. 2) - Supporting Activity: JAEA has improved the effectiveness and efficiency of existing safeguards activities. The Integrated Safeguards approach for all facilities in NCL has been implemented since August, 2008, as a pioneer and a good example in the world. To reduce anxiety among local residents, NCL has explained its operation plans and exchanged information and opinions with them concerning potential risks to health and environment. Recently, stake-holder participation in the management of NCL was started from the view point of Corporate Social Responsibility. In April, 2008, the agreement was signed with Idaho National Laboratory for cooperation of personnel training in fuel cycle area. 3. Mid-Term Direction: In Japan, feasibility and direction of the transition period from the LWR era to the FBR era should be discussed for the next several years. Study

  16. Direct catalytic trifluoromethylthiolation of boronic acids and alkynes employing electrophilic shelf-stable N-(trifluoromethylthio)phthalimide.

    Science.gov (United States)

    Pluta, Roman; Nikolaienko, Pavlo; Rueping, Magnus

    2014-02-03

    A new and safe method for the synthesis of N-(trifluoromethylthio)phthalimide, a convenient and shelf-stable reagent for the direct trifluoromethylthiolation, has been developed. N-(Trifluoromethylthio)phthalimide can be used as an electrophilic source of F3 CS(+) and reacts readily with boronic acids and alkynes under copper catalysis. The utility of CF3 S-containing molecules as biologically active agents, the mild reaction conditions employed, and the high tolerance of functional groups demonstrate the potential of this new methodology to be widely applied in organic synthesis as well as industrial pharmaceutical and agrochemical research and development. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Catalytic treatment

    Energy Technology Data Exchange (ETDEWEB)

    Bindley, W T.R.

    1931-04-18

    An apparatus is described for the catalytic treatment of liquids, semi-liquids, and gases comprising a vessel into which the liquid, semi-liquid, or gas to be treated is introduced through a common inlet to a chamber within the vessel whence it passes to contact with a catalyst through radially arranged channels or passages to a common outlet chamber.

  18. Design of a PWR for long cycle and direct recycling of spent fuel

    Energy Technology Data Exchange (ETDEWEB)

    Mohamed, Nader M.A., E-mail: mnader73@yahoo.com

    2015-12-15

    Highlights: • Single-batch loading PWR with a new fuel assembly for 36 calendar months cycle was designed. • The new fuel assembly is constructed from a number of CANDU fuel bundles. • This design enables to recycle the spent fuel directly in CANDU reactors for high burnup. • Around 56 MWd/kgU burnup is achieved from fuel that has average enrichment of 4.8 w/o U-235 using this strategy. • Safety parameters such as the power distribution and CANDU coolant void reactivity were considered. - Abstract: In a previous work, a new design was proposed for the Pressurized Water Reactor (PWR) fuel assembly for direct use of the PWR spent fuel without processing. The proposed assembly has four zircaloy-4 tubes contains a number of 61-element CANDU fuel bundles (8 bundles per tube) stacked end to end. The space between the tubes contains 44 lower enriched UO{sub 2} fuel rods and 12 guide tubes. In this paper, this assembly is used to build a single batch loading 36-month PWR and the spent CANDU bundles are recycled in the on power refueling CANDU reactors. The Advanced PWR (APWR) is considered as a reference design. The average enrichment in the core is 4.76%w U-235. IFBA and Gd{sub 2}O{sub 3} as burnable poisons are used for controlling the excess reactivity and to flatten the power distribution. The calculations using MCNPX showed that the PWR will discharge the fuel with average burnup of 31.8 MWd/kgU after 1000 effective full power days. Assuming a 95 days plant outage, 36 calendar months can be achieved with a capacity factor of 91.3%. Good power distribution in the core is obtained during the cycle and the required critical boron concentration is less than 1750 ppm. Recycling of the discharged CANDU fuel bundles that represents 85% of the fuel in the assembly, in CANDU-6 or in 700 MWe Advanced CANDU Reactor (ACR-700), an additional burnup of about 31 or 26 MWd/kgU burnup can be achieved, respectively. Averaging the fuel burnup on the all fuel in the PWR

  19. Direct radioimmunoassay of urinary estrogen and pregnanediol glucuronides during the menstrual cycle

    International Nuclear Information System (INIS)

    Stanczyk, F.Z.; Miyakawa, I.; Goebelsmann, U.

    1980-01-01

    Assays measuring immunoreactive estrone glucuronide (E 1 G), estradiol-3-glucuronide (E 2 -3G), estradiol-17β-glucuronide (E 2 -17G), estriol-3-glucuronide (E 3 -3G), estriol-16α-glucuronide (E 3 -16G), and pregnanediol-3α-glucuronide (Pd-3G) directly in diluted urine were developed and validated. These estrogen and pregnanediol glucuronide fractions were measured in aliquots of 24-hour and overnight samples of urine collected daily from seven women for one menstrual cycle. Urinary hormone excretion was correlated with daily serum estradiol (E 2 ), progesterone (P), and lutenizing hormonee (LH) levels. A sharp midcycle LH peak preceded by a preovulatory rise in serum E 2 and followed by luteal phase serum P levels were noted in each of the seven apparently ovulatory cycles. Twenty-four-hour and overnight urinary excretion patterns of estrogen glucuronides were similar to those of serum E 2 . Of the five estrogen glucuronide fractions tested, excretion of E 2 -17G exhibited the earliest and steepest ascending slope of the preovulatory estrogen surge and correlated best with serum E 2 levels. Urinary excretion of E 1 -G, E 2 -3G, and E 3 -16G also showed an early and steep preovulatory rise and preceded that of E 3 -3G, whereas urinary excretion of E 3 -3G exhibited the poorest correlation with serum E 2 concentrations. The urinary excretion of Pd-3G rose parallel to serum P levels and was markedly elevated 2 to 3 days after the midcycle LH peak in both 24-hour and overnight collections of urine. These results indicate that among the urinary estrogen conjugate fractions tested, E 2 -17G is the one that most suitably predicts ovulation

  20. Performance analysis of a Kalina cycle for a central receiver solar thermal power plant with direct steam generation

    International Nuclear Information System (INIS)

    Modi, Anish; Haglind, Fredrik

    2014-01-01

    Solar thermal power plants have attracted increasing interest in the past few years – with respect to both the design of the various plant components, and extending the operation hours by employing different types of storage systems. One approach to improve the overall plant efficiency is to use direct steam generation with water/steam as both the heat transfer fluid in the solar receivers and the cycle working fluid. This enables operating the plant with higher turbine inlet temperatures. Available literature suggests that it is feasible to use ammonia-water mixtures at high temperatures without corroding the equipment by using suitable additives with the mixture. The purpose of the study reported here was to investigate if there is any benefit of using a Kalina cycle for a direct steam generation, central receiver solar thermal power plant with high live steam temperature (450 °C) and pressure (over 100 bar). Thermodynamic performance of the Kalina cycle in terms of the plant exergy efficiency was evaluated and compared with a simple Rankine cycle. The rates of exergy destruction for the different components in the two cycles were also calculated and compared. The results suggest that the simple Rankine cycle exhibits better performance than the Kalina cycle when the heat input is only from the solar receiver. However, when using a two-tank molten-salt storage system as the primary source of heat input, the Kalina cycle showed an advantage over the simple Rankine cycle because of about 33 % reduction in the storage requirement. The solar receiver showed the highest rate of exergy destruction for both the cycles. The rates of exergy destruction in other components of the cycles were found to be highly dependent on the amount of recuperation, and the ammonia mass fraction and pressure at the turbine inlet. - Highlights: •Kalina cycle for a central receiver solar thermal power plant with direct steam generation. •Rankine cycle shows better plant exergy

  1. MOTHER MK II: An advanced direct cycle high temperature gas reactor

    International Nuclear Information System (INIS)

    Hart, R.S.; Kendall, J.M.; Marsden, B.J.

    2003-01-01

    The MOTHER (MOdular Thermal HElium Reactor) power plant concepts employ high temperature gas reactors utilizing TRISO fuel, graphite moderator, and helium coolant, in combination with a direct Brayton cycle for electricity generation. The helium coolant from the reactor vessel passes through a Power Conversion Unit (PCU), which includes a turbine-generator, recuperator, precooler, intercooler and turbine-compressors, before being returned to the reactor vessel. The PCU substitutes for the reactor coolant system pumps and steam generators and most of the Balance Of Plant (BOP), including the steam turbines and condensers, employed by conventional nuclear power plants utilizing water cooled reactors. This provides a compact, efficient, and relatively simple plant configuration. The MOTHER MK I conceptual design, completed in the 1987 - 1989 time frame, was developed to economically meet the energy demands for extracting and processing heavy oil from the tar sands of western Canada. However, considerable effort was made to maximize the market potential beyond this application. Consistent with the remote and very high labour rate environment in the tar sands region, simplification of maintenance procedures and facilitation of 'change-out' in lieu of in situ repair was a design focus. MOTHER MK I had a thermal output of 288 MW and produced 120 MW electrical when operated in the electricity only production mode. An annular Prismatic reactor core was utilized, largely to minimize day-to-day operations activities. Key features of the power conversion system included two Power Conversion Units (144 MW th each), the horizontal orientation of all rotating machinery and major heat exchangers axes, high speed rotating machinery (17,030 rpm for the turbine-compressors and 10,200 rpm for the power turbine-generator), gas (helium) bearings for all rotating machinery, and solid state frequency conversion from 170 cps (at full power) to the grid frequency. Recognizing that the on

  2. High temperature high velocity direct power extraction using an open-cycle oxy-combustion system

    Energy Technology Data Exchange (ETDEWEB)

    Love, Norman [Univ. of Texas, El Paso, TX (United States)

    2017-09-29

    The implementation of oxy-fuel technology in fossil-fuel power plants may contribute to increased system efficiencies and a reduction of pollutant emissions. One technology that has potential to utilize the temperature of undiluted oxy-combustion flames is open-cycle magnetohydrodynamic (MHD) power generators. These systems can be configured as a topping cycle and provide high enthalpy, electrically conductive flows for direct conversion of electricity. This report presents the design and modeling strategies of a MHD combustor operating at temperatures exceeding 3000 K. Throughout the study, computational fluid dynamics (CFD) models were extensively used as a design and optimization tool. A lab-scale 60 kWth model was designed, manufactured and tested as part of this project. A fully-coupled numerical method was developed in ANSYS FLUENT to characterize the heat transfer in the system. This study revealed that nozzle heat transfer may be predicted through a 40% reduction of the semi-empirical Bartz correlation. Experimental results showed good agreement with the numerical evaluation, with the combustor exhibiting a favorable performance when tested during extended time periods. A transient numerical method was employed to analyze fuel injector geometries for the 60-kW combustor. The ANSYS FLUENT study revealed that counter-swirl inlets achieve a uniform pressure and velocity ratio when the ports of the injector length to diameter ratio (L/D) is 4. An angle of 115 degrees was found to increase distribution efficiency. The findings show that this oxy-combustion concept is capable of providing a high-enthalpy environment for seeding, in order to render the flow to be conductive. Based on previous findings, temperatures in the range of 2800-3000 K may enable magnetohydrodynamic power extraction. The heat loss fraction in this oxy-combustion system, based on CFD and analytical calculations, at optimal operating conditions, was estimated to be less than 10 percent

  3. Assessing eco-efficiency: A metafrontier directional distance function approach using life cycle analysis

    International Nuclear Information System (INIS)

    Beltrán-Esteve, Mercedes; Reig-Martínez, Ernest; Estruch-Guitart, Vicent

    2017-01-01

    Sustainability analysis requires a joint assessment of environmental, social and economic aspects of production processes. Here we propose the use of Life Cycle Analysis (LCA), a metafrontier (MF) directional distance function (DDF) approach, and Data Envelopment Analysis (DEA), to assess technological and managerial differences in eco-efficiency between production systems. We use LCA to compute six environmental and health impacts associated with the production processes of nearly 200 Spanish citrus farms belonging to organic and conventional farming systems. DEA is then employed to obtain joint economic-environmental farm's scores that we refer to as eco-efficiency. DDF allows us to determine farms' global eco-efficiency scores, as well as eco-efficiency scores with respect to specific environmental impacts. Furthermore, the use of an MF helps us to disentangle technological and managerial eco-inefficiencies by comparing the eco-efficiency of both farming systems with regards to a common benchmark. Our core results suggest that the shift from conventional to organic farming technology would allow a potential reduction in environmental impacts of 80% without resulting in any decline in economic performance. In contrast, as regards farmers' managerial capacities, both systems display quite similar mean scores.

  4. Assessing eco-efficiency: A metafrontier directional distance function approach using life cycle analysis

    Energy Technology Data Exchange (ETDEWEB)

    Beltrán-Esteve, Mercedes, E-mail: mercedes.beltran@uv.es [Department of Applied Economics II, University of Valencia (Spain); Reig-Martínez, Ernest [Department of Applied Economics II, University of Valencia, Ivie (Spain); Estruch-Guitart, Vicent [Department of Economy and Social Sciences, Polytechnic University of Valencia (Spain)

    2017-03-15

    Sustainability analysis requires a joint assessment of environmental, social and economic aspects of production processes. Here we propose the use of Life Cycle Analysis (LCA), a metafrontier (MF) directional distance function (DDF) approach, and Data Envelopment Analysis (DEA), to assess technological and managerial differences in eco-efficiency between production systems. We use LCA to compute six environmental and health impacts associated with the production processes of nearly 200 Spanish citrus farms belonging to organic and conventional farming systems. DEA is then employed to obtain joint economic-environmental farm's scores that we refer to as eco-efficiency. DDF allows us to determine farms' global eco-efficiency scores, as well as eco-efficiency scores with respect to specific environmental impacts. Furthermore, the use of an MF helps us to disentangle technological and managerial eco-inefficiencies by comparing the eco-efficiency of both farming systems with regards to a common benchmark. Our core results suggest that the shift from conventional to organic farming technology would allow a potential reduction in environmental impacts of 80% without resulting in any decline in economic performance. In contrast, as regards farmers' managerial capacities, both systems display quite similar mean scores.

  5. Systems design of direct-cycle supercritical-water-cooled fast reactors

    International Nuclear Information System (INIS)

    Oka, Yoshiaki; Koshizuka, Seiichi; Jevremovic, Tatjana; Okano, Yashushi

    1995-01-01

    The system design of a direct-cycle supercritical-water-cooled fast reactor is presented. The supercritical water does not exhibit a change of phase. the recirculation system, steam separator, and dryer of a boiling water reactor (BWR) are unnecessary. Roughly speaking, the reactor pressure vessel and control rods are similar to those of a pressurized water reactor, the containment and emergency core cooling system are similar to a BWR, and the balance of plant is similar to a supercritical-pressure fossil-fired power plant (FPP). the electric power of the fast converter is 1,508 MW(electric). The number of coolant loops is only two because of the high coolant enthalpy. Containment volume is much reduced. The thermal efficiency is improved 24% over a BWR. The coolant void reactivity is negative by placing thin zirconium-hydride layers between seeds and blankets. The power costs would be much reduced compared with those of a light water reactor (LWR) and a liquid-metal fast breeder reactor. The concept is based on the huge amount of experience with the water coolant technology of LWRs and FPPs. The oxidation of stainless steel cladding is avoided by adopting a much lower coolant temperature than that of the FPP

  6. High temperature low cycle fatigue behavior of a directionally solidified Ni-base superalloy DZ951

    International Nuclear Information System (INIS)

    Chu Zhaokuang; Yu Jinjiang; Sun Xiaofeng; Guan Hengrong; Hu Zhuangqi

    2008-01-01

    Total strain-controlled low cycle fatigue (LCF) tests were performed at a temperature range from 700 to 900 deg. C in ambient air condition on a directionally solidified Ni-base superalloy DZ951. The fatigue life of DZ951 alloy does not monotonously decrease with increasing temperature, but exhibits a strong dependence on the total strain range. The dislocation characteristics and failed surface observation were evaluated through transmission electron microscopy and scanning electron microscopy. The alloy exhibits cyclic hardening, softening or cyclic stability as a whole, which is dependent on the testing temperature and total strain range. At 700 deg. C, the cyclic plastic deformation process is the main cause of fatigue failure. At 900 deg. C, the failure mostly results from combined fatigue and creep damage under total strain range from 0.6 to 1.2% and the reduction in fatigue life can be taken as the cause of oxidation, creep and cyclic plastic deformation under total strain range of 0.5%

  7. Current status and future direction of INPRO (International Project on Innovative Nuclear Reactors and Fuel Cycles)

    International Nuclear Information System (INIS)

    Omoto, Akira; Moriwaki, Masanao; Sugimoto, Jun; Nakai, Ryodai

    2007-01-01

    INPRO is an international forum to consider jointly the international and national actions required to achieve desired innovations in nuclear reactors and fuel cycles so as to ensure that nuclear energy is available to contribute to a sustainable development of the human, and IAEA becomes the secretariat for INPRO. The number of the members counts 28 by recent participation of Japan and U.S.A. now, and it is a unique forum to bring together both technology users and technology holders, that includes 5 countries which do not still have nuclear power generation. Until now it was phase I, and focused its activities to make clear the desired characteristics of nuclear energy system toward the future, and to develop methodology to evaluate various nuclear energy systems, but it shifted to phase II from July, 2006, and it planned three areas of activities such as improvement of evaluation methodology, institutional/infrastructure oriented activities and a collaborative project of technology development. Current status and future direction of INPRO was presented to encourage Japan in significant contributions of these three areas. (T. Tanaka)

  8. Diurnal cycle of the dust instantaneous direct radiative forcing over the Arabian Peninsula

    KAUST Repository

    Osipov, Sergey

    2015-08-27

    In this study we attempted to better quantify radiative effects of dust over the Arabian Peninsula and their dependence on input parameters. For this purpose we have developed a stand-alone column radiation transport model coupled with the Mie, T-matrix and geometric optics calculations and driven by reanalysis meteorological fields and atmospheric composition. Numerical experiments were carried out for a wide range of aerosol optical depths, including extreme values developed during the dust storm on 18–20 March 2012. Comprehensive ground-based observations and satellite retrievals were used to estimate aerosol optical properties, validate calculations and carry out radiation closure. The broadband surface albedo, fluxes at the bottom and top of the atmosphere as well as instantaneous dust radiative forcing were estimated both from the model and observations. Diurnal cycle of the shortwave instantaneous dust direct radiative forcing was studied for a range of aerosol and surface characteristics representative of the Arabian Peninsula. Mechanisms and parameters responsible for diurnal variability of the radiative forcing were evaluated. We found that intrinsic variability of the surface albedo and its dependence on atmospheric conditions, along with anisotropic aerosol scattering, are mostly responsible for diurnal effects.

  9. Direct radioimmunoassay of urinary estrogen and pregnanediol glucuronides during the menstrual cycle

    Energy Technology Data Exchange (ETDEWEB)

    Stanczyk, F.Z.; Miyakawa, I.; Goebelsmann, U.

    1980-06-15

    Assays measuring immunoreactive estrone glucuronide (E/sub 1/G), estradiol-3-glucuronide (E/sub 2/-3G), estradiol-17..beta..-glucuronide (E/sub 2/-17G), estriol-3-glucuronide (E/sub 3/-3G), estriol-16..cap alpha..-glucuronide (E/sub 3/-16G), and pregnanediol-3..cap alpha..-glucuronide (Pd-3G) directly in diluted urine were developed and validated. These estrogen and pregnanediol glucuronide fractions were measured in aliquots of 24-hour and overnight samples of urine collected daily from seven women for one menstrual cycle. Urinary hormone excretion was correlated with daily serum estradiol (E/sub 2/), progesterone (P), and lutenizing hormonee (LH) levels. A sharp midcycle LH peak preceded by a preovulatory rise in serum E/sub 2/ and followed by luteal phase serum P levels were noted in each of the seven apparently ovulatory cycles. Twenty-four-hour and overnight urinary excretion patterns of estrogen glucuronides were similar to those of serum E/sub 2/. Of the five estrogen glucuronide fractions tested, excretion of E/sub 2/-17G exhibited the earliest and steepest ascending slope of the preovulatory estrogen surge and correlated best with serum E/sub 2/ levels. Urinary excretion of E/sub 1/-G, E/sub 2/-3G, and E/sub 3/-16G also showed an early and steep preovulatory rise and preceded that of E/sub 3/-3G, whereas urinary excretion of E/sub 3/-3G exhibited the poorest correlation with serum E/sub 2/ concentrations. The urinary excretion of Pd-3G rose parallel to serum P levels and was markedly elevated 2 to 3 days after the midcycle LH peak in both 24-hour and overnight collections of urine. These results indicate that among the urinary estrogen conjugate fractions tested, E/sub 2/-17G is the one that most suitably predicts ovulation.

  10. Comparison of Heat Transfer Fluid and Direct Steam Generation technologies for Integrated Solar Combined Cycles

    International Nuclear Information System (INIS)

    Rovira, Antonio; Montes, María José; Varela, Fernando; Gil, Mónica

    2013-01-01

    At present time and in the medium term, Solar Thermal Power Plants are going to share scenario with conventional energy generation technologies, like fossil and nuclear. In such a context, Integrated Solar Combined Cycles (ISCCs) may be an interesting choice since integrated designs may lead to a very efficient use of the solar and fossil resources. In this work, different ISCC configurations including a solar field based on parabolic trough collectors and working with the so-called Heat Transfer Fluid (HTF) and Direct Steam Generation (DSG) technologies are compared. For each technology, four layouts have been studied: one in which solar heat is used to evaporate part of the high pressure steam of a bottoming Rankine cycle with two pressure levels, another that incorporates a preheating section to the previous layout, the third one that includes superheating instead of preheating and the last one including both preheating and superheating in addition to the evaporation. The analysis is made with the aim of finding out which of the different layouts reaches the best performance. For that purpose, three types of comparisons have been performed. The first one assesses the benefits of including a solar steam production fixed at 50 MW th . The second one compares the configurations with a standardised solar field size instead of a fixed solar steam production. Finally, the last one consists on an even more homogeneous comparison considering the same steam generator size for all the configurations as well as standardised solar fields. The configurations are studied by mean of exergy analyses. Several figures of merit are used to correctly assess the configurations. Results reveal that the only-evaporative DSG configuration becomes the best choice, since it benefits of both low irreversibility at the heat recovery steam generator and high thermal efficiency in the solar field. Highlights: ► ISCC configurations with DSG and HTF technologies are compared. ► Four

  11. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  12. A direct estimate of evapotranspiration over the Amazon basin and implications for our understanding of carbon and water cycling

    Science.gov (United States)

    Swann, A. L. S.; Koven, C.; Lombardozzi, D.; Bonan, G. B.

    2017-12-01

    Evapotranspiration (ET) is a critical term in the surface energy budget as well as the water cycle. There are few direct measurements of ET, and thus the magnitude and variability is poorly constrained at large spatial scales. Estimates of the annual cycle of ET over the Amazon are critical because they influence predictions of the seasonal cycle of carbon fluxes, as well as atmospheric dynamics and circulation. We estimate ET for the Amazon basin using a water budget approach, by differencing rainfall, discharge, and time-varying storage from the Gravity Recovery and Climate Experiment. We find that the climatological annual cycle of ET over the Amazon basin upstream of Óbidos shows suppression of ET during the wet season, and higher ET during the dry season, consistent with flux tower based observations in seasonally dry forests. We also find a statistically significant decrease in ET over the time period 2002-2015 of -1.46 mm/yr. Our direct estimate of the seasonal cycle of ET is largely consistent with previous indirect estimates, including energy budget based approaches, an up-scaled station based estimate, and land surface model estimates, but suggests that suppression of ET during the wet season is underestimated by existing products. We further quantify possible contributors to the phasing of the seasonal cycle and downward time trend using land surface models.

  13. Optimisation of a Kalina cycle for a central receiver solar thermal power plant with direct steam generation

    DEFF Research Database (Denmark)

    Modi, Anish; Haglind, Fredrik

    2014-01-01

    Central receiver solar thermal power plants are regarded as one of the promising ways to generate electricity in near future. They offer the possibility of using high temperatures and pressures to achieve high efficiencies with standard power cycles. A direct steam generation approach can be used...

  14. Influences of Scholarship Aid on the Social Exchange Cycle: A Qualitative Exploration of Scholarship Recipients and Direct Reciprocity

    Science.gov (United States)

    Forrest, Jeannie

    2010-01-01

    Social exchange theory asserts that individuals who receive a gift will be pressed by an internal sense of obligation to give back in turn (Mauss, 2002). While there is a great deal of literature devoted to giving, there is little literature about the receiving end of the exchange cycle. Deeply impacted by the effects of direct reciprocity are…

  15. Immobilization of glucose oxidase onto a novel platform based on modified TiO{sub 2} and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Nasibeh, E-mail: Haghighi.nasibeh@yahoo.com [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Hallaj, Rahman, E-mail: Rhallaj@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Nanotechnology Research Center, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2017-04-01

    In this work a new organic–inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO{sub 2}) modified with 2, 2′-dithioxo-3, 3′-bis (3-(triethoxysilyl) propyl)-2H, 2′H-[5, 5′-bithiazolylidene]-4, 4′(3H, 3′H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO{sub 2} nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO{sub 2}-OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of − 0.465 V and an apparent electron transfer rate constant of 1.74 s{sup −1}. The GO/TiO{sub 2}-OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO{sub 2}-OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. - Highlights: • In this work a novel platform used to successful immobilization of glucose oxidase. Due to its large functional group this modified nanoparticles load enzyme (GOD) and remain enzyme whit out denaturation for a long time. • The loaded enzyme shows direct electron transfer and excellent charge transfer kinetic. Also the fabricated nano-bio-composite has good catalytic activity toward hydrogen peroxide during electrooxidation and electro reduction process. • The nano-bio-composite shows excellent photocatalytic activity.

  16. Immobilization of glucose oxidase onto a novel platform based on modified TiO2 and graphene oxide, direct electrochemistry, catalytic and photocatalytic activity

    International Nuclear Information System (INIS)

    Haghighi, Nasibeh; Hallaj, Rahman; Salimi, Abdollah

    2017-01-01

    In this work a new organic–inorganic nanocomposite has been introduced for enzyme immobilization. The composite consisting of graphene oxide (GO) and titanium oxide nanoparticles (TiO 2 ) modified with 2, 2′-dithioxo-3, 3′-bis (3-(triethoxysilyl) propyl)-2H, 2′H-[5, 5′-bithiazolylidene]-4, 4′(3H, 3′H)-dione as Organic-Inorganic Supporting Ligand (OISL). The OISL was covalently attached to TiO 2 nanoparticles and employed for obtaining a suitable solid surface to enzyme attachment. The glucose oxidase (GOD) was irreversibly loaded on the GC/GO/TiO 2 -OISL using consecutive cyclic voltammetry. The enzyme immobilization and the enzymatic activity were determined by electrochemical methods. The cyclic voltammogram displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of − 0.465 V and an apparent electron transfer rate constant of 1.74 s −1 . The GO/TiO 2 -OISL can catalyze the electroreduction and electrooxidation of hydrogen peroxide. The GC/GO/TiO 2 -OISL/GOD electrode was used in the hydrogen peroxide determination. The fabricated nanobiocomposite shows dramatic photoelectrocatalytic activity which evaluated by studying the electrocatalytic activity of the fabricated electrode toward hydrogen peroxide in darkness and in the presences of light. - Highlights: • In this work a novel platform used to successful immobilization of glucose oxidase. Due to its large functional group this modified nanoparticles load enzyme (GOD) and remain enzyme whit out denaturation for a long time. • The loaded enzyme shows direct electron transfer and excellent charge transfer kinetic. Also the fabricated nano-bio-composite has good catalytic activity toward hydrogen peroxide during electrooxidation and electro reduction process. • The nano-bio-composite shows excellent photocatalytic activity.

  17. Co-catalytic effect of Ni in the methanol electro-oxidation on Pt-Ru/C catalyst for direct methanol fuel cell

    International Nuclear Information System (INIS)

    Wang, Z.B.; Yin, G.P.; Zhang, J.; Sun, Y.C.; Shi, P.F.

    2006-01-01

    This research is aimed to improve the utilization and activity of anodic catalysts, thus to lower the contents of noble metals loading in anodes for methanol electro-oxidation. The direct methanol fuel cell anodic catalysts, Pt-Ru-Ni/C and Pt-Ru/C, were prepared by chemical reduction method. Their performances were tested by using a glassy carbon working electrode through cyclic voltammetric curves, chronoamperometric curves and half-cell measurement in a solution of 0.5 mol/L CH 3 OH and 0.5 mol/L H 2 SO 4 . The composition of the Pt-Ru-Ni and Pt-Ru surface particles were determined by EDAX analysis. The particle size and lattice parameter of the catalysts were determined by means of X-ray diffraction (XRD). XRD analysis showed that both of the catalysts exhibited face-centered cubic structures and had smaller lattice parameters than Pt-alone catalyst. Their sizes are small, about 4.5 nm. No significant differences in the methanol electro-oxidation on both electrodes were found by using cyclic voltammetry, especially regarding the onset potential for methanol electro-oxidation. The electrochemically active-specific areas of the Pt-Ru-Ni/C and Pt-Ru/C catalysts are almost the same. But, the catalytic activity of the Pt-Ru-Ni/C catalyst is higher for methanol electro-oxidation than that of the Pt-Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol electro-oxidation is better than that of the Pt-Ru/C catalyst

  18. Preparation method of Ni@Pt/C nanocatalyst affects the performance of direct borohydride-hydrogen peroxide fuel cell: Improved power density and increased catalytic oxidation of borohydride.

    Science.gov (United States)

    Hosseini, Mir Ghasem; Mahmoodi, Raana

    2017-08-15

    The Ni@Pt/C electrocatalysts were synthesized using two different methods: with sodium dodecyl sulfate (SDS) and without SDS. The metal loading in synthesized nanocatalysts was 20wt% and the molar ratio of Ni: Pt was 1:1. The structural characterizations of Ni@Pt/C electrocatalysts were investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HR-TEM). The electrocatalytic activity of Ni@Pt/C electrocatalysts toward BH 4 - oxidation in alkaline medium was studied by means of cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results showed that Ni@Pt/C electrocatalyst synthesized without SDS has superior catalytic activity toward borohydride oxidation (22016.92Ag Pt -1 ) in comparison with a catalyst prepared in the presence of SDS (17766.15Ag Pt -1 ) in NaBH 4 0.1M at 25°C. The Membrane Electrode Assembly (MEA) used in fuel cell set-up was fabricated with catalyst-coated membrane (CCM) technique. The effect of Ni@Pt/C catalysts prepared with two methods as anode catalyst on the performance of direct borohydride-hydrogen peroxide fuel cell was studied. The maximum power density was obtained using Ni@Pt/C catalyst synthesized without SDS at 60°C, 1M NaBH 4 and 2M H 2 O 2 (133.38mWcm -2 ). Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Population exposure from the nuclear fuel cycle: Review and future direction

    International Nuclear Information System (INIS)

    Richmond, C.R.

    1988-01-01

    The legacy of radiation exposures confronting man arises from two historical sources of energy, the sun and radioactive decay. Contemporary man continues to be dependent on these two energy sources, which include the nuclear fuel cycle. Radiation exposures from all energy sources should be examined, with particular emphasis on the nuclear fuel cycle, including incidents such as Chernobyl and Three Mile Island. In addition to risk estimation, concepts such as de minimis, life shortening as a measure of risk, and competing risks as projected into the future must be considered in placing radiation exposures in perspective. The utility of these concepts is in characterizing population exposures for decision makers in a manner that the public may judge acceptable. All these viewpoints are essential in the evaluation of population exposure from the nuclear fuel cycle

  20. Mechanism of Diphtheria Toxin Catalytic Domain Delivery to the Eukaryotic Cell Cytosol and the Cellular Factors that Directly Participate in the Process

    Science.gov (United States)

    Murphy, John R.

    2011-01-01

    Research on diphtheria and anthrax toxins over the past three decades has culminated in a detailed understanding of their structure function relationships (e.g., catalytic (C), transmembrane (T), and receptor binding (R) domains), as well as the identification of their eukaryotic cell surface receptor, an understanding of the molecular events leading to the receptor-mediated internalization of the toxin into an endosomal compartment, and the pH triggered conformational changes required for pore formation in the vesicle membrane. Recently, a major research effort has been focused on the development of a detailed understanding of the molecular interactions between each of these toxins and eukaryotic cell factors that play an essential role in the efficient translocation of their respective catalytic domains through the trans-endosomal vesicle membrane pore and delivery into the cell cytosol. In this review, I shall focus on recent findings that have led to a more detailed understanding of the mechanism by which the diphtheria toxin catalytic domain is delivered to the eukaryotic cell cytosol. While much work remains, it is becoming increasingly clear that the entry process is facilitated by specific interactions with a number of cellular factors in an ordered sequential fashion. In addition, since diphtheria, anthrax lethal factor and anthrax edema factor all carry multiple coatomer I complex binding motifs and COPI complex has been shown to play an essential role in entry process, it is likely that the initial steps in catalytic domain entry of these divergent toxins follow a common mechanism. PMID:22069710

  1. Energy and exergy analysis of the Kalina cycle for use in concentrated solar power plants with direct steam generation

    DEFF Research Database (Denmark)

    Knudsen, Thomas; Clausen, Lasse Røngaard; Haglind, Fredrik

    2014-01-01

    In concentrated solar power plants using direct steam generation, the usage of a thermal storage unit based only on sensible heat may lead to large exergetic losses during charging and discharging, due to a poor matching of the temperature profiles. By the use of the Kalina cycle, in which...... evaporation and condensation takes place over a temperature range, the efficiency of the heat exchange processes can be improved, possibly resulting also in improved overall performance of the system. This paper is aimed at evaluating the prospect of using the Kalina cycle for concentrated solar power plants...... with direct steam generation. The following two scenarios were addressed using energy and exergy analysis: generating power using heat from only the receiver and using only stored heat. For each of these scenarios comparisons were made for mixture concentrations ranging from 0.1 mole fraction of ammonia to 0...

  2. Effect of thermal cycling on the microstructure of a directionally solidified Fe, Cr, Al-TaC eutectic alloy

    Science.gov (United States)

    Harf, F. H.; Tewari, S. N.

    1977-01-01

    Cylindrical bars (1.2 cm diameter) of Fe-13.6Cr-3.7Al-9TaC (wt %) eutectic alloy were directionally solidified in a modified Bridgman type furnace at 1 cm/h. The alloy microstructure consisted of aligned TaC fibers imbedded in a bcc Fe-Cr-Al matrix. Specimens of the alloy were thermally cycled from 1100 to 425 C in a burner rig. The effects of 1800 thermal cycles on the microstructure was examined by scanning electron microscopy, revealing a zig-zag shape of TaC fibers aligned parallel to the growth direction. The mechanism of carbide solution and reprecipitation on the (111) easy growth planes, suggested previously to account for the development of irregular serrations in Co-Cr-Ni matrix alloys, is believed to be responsible for these zig-zag surfaces.

  3. Results of the German alternative fuel cycle evaluation and further efforts geared toward demonstration of direct disposal

    International Nuclear Information System (INIS)

    Papp, R.; Closs, K.D.

    1986-01-01

    In a comparative study initiated by the German Federal Ministry for Research and Technology which was carried out by Karlsruhe Nuclear Research Center in the period from 1981 to 1985, direct disposal of spent fuel was contrasted to the traditional fuel cycle with reprocessing and recycle. The results of the study did not exhibit decisive advantages of direct disposal over fuel reprocessing. Due to this face and legal requirements of the German Atomic Energy Act, the cabinet concluded to continue to adhere to fuel reprocessing as the preferred version of ''Entsorgung''. But the door was left ajar for the direct disposal alternative that, under present atomic law, is permissible for fuel for which reprocessing is neither technically feasible nor economically justified. An ambitious program has been launched in the Federal Republic of Germany (FRG), geared to bring direct disposal to a point of technical maturity

  4. Automatic cardiac cycle determination directly from EEG-fMRI data by multi-scale peak detection method.

    Science.gov (United States)

    Wong, Chung-Ki; Luo, Qingfei; Zotev, Vadim; Phillips, Raquel; Chan, Kam Wai Clifford; Bodurka, Jerzy

    2018-03-31

    In simultaneous EEG-fMRI, identification of the period of cardioballistic artifact (BCG) in EEG is required for the artifact removal. Recording the electrocardiogram (ECG) waveform during fMRI is difficult, often causing inaccurate period detection. Since the waveform of the BCG extracted by independent component analysis (ICA) is relatively invariable compared to the ECG waveform, we propose a multiple-scale peak-detection algorithm to determine the BCG cycle directly from the EEG data. The algorithm first extracts the high contrast BCG component from the EEG data by ICA. The BCG cycle is then estimated by band-pass filtering the component around the fundamental frequency identified from its energy spectral density, and the peak of BCG artifact occurrence is selected from each of the estimated cycle. The algorithm is shown to achieve a high accuracy on a large EEG-fMRI dataset. It is also adaptive to various heart rates without the needs of adjusting the threshold parameters. The cycle detection remains accurate with the scan duration reduced to half a minute. Additionally, the algorithm gives a figure of merit to evaluate the reliability of the detection accuracy. The algorithm is shown to give a higher detection accuracy than the commonly used cycle detection algorithm fmrib_qrsdetect implemented in EEGLAB. The achieved high cycle detection accuracy of our algorithm without using the ECG waveforms makes possible to create and automate pipelines for processing large EEG-fMRI datasets, and virtually eliminates the need for ECG recordings for BCG artifact removal. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  5. A catalytic approach to estimate the redox potential of heme-peroxidases

    International Nuclear Information System (INIS)

    Ayala, Marcela; Roman, Rosa; Vazquez-Duhalt, Rafael

    2007-01-01

    The redox potential of heme-peroxidases varies according to a combination of structural components within the active site and its vicinities. For each peroxidase, this redox potential imposes a thermodynamic threshold to the range of oxidizable substrates. However, the instability of enzymatic intermediates during the catalytic cycle precludes the use of direct voltammetry to measure the redox potential of most peroxidases. Here we describe a novel approach to estimate the redox potential of peroxidases, which directly depends on the catalytic performance of the activated enzyme. Selected p-substituted phenols are used as substrates for the estimations. The results obtained with this catalytic approach correlate well with the oxidative capacity predicted by the redox potential of the Fe(III)/Fe(II) couple

  6. Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

    Science.gov (United States)

    Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

    1986-01-01

    This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

  7. Promising Direction of Perfection of the Utilization Combine Cycle Gas Turbine Units

    Directory of Open Access Journals (Sweden)

    Gabdullina Albina I.

    2017-01-01

    Full Text Available Issues of improving the efficiency of combined cycle gas turbines (CCGT recovery type have been presented. Efficiency gas turbine plant reaches values of 45 % due to rise in temperature to a gas turbine to 1700 °C. Modern technologies for improving the cooling gas turbine components and reducing the excess air ratio leads to a further increase of the efficiency by 1-2 %. Based on research conducted at the Tomsk Polytechnic University, it shows that the CCGT efficiency can be increased by 2-3 % in the winter time due to the use of organic Rankine cycle, low-boiling substances, and air-cooled condensers (ACC. It is necessary to apply the waste heat recovery with condensation of water vapor from the flue gas, it will enhance the efficiency of the CCGT by 2-3 % to increase the efficiency of the heat recovery steam boiler (HRSB to 10-12 %. Replacing electric pumps gas turbine engine (GTE helps to reduce electricity consumption for auxiliary needs CCGT by 0.5-1.5 %. At the same time the heat of flue gas turbine engine may be useful used in HRSB, thus will increase the capacity and efficiency of the steam turbine.

  8. Pressure transients analysis of a high-temperature gas-cooled reactor with direct helium turbine cycle

    Energy Technology Data Exchange (ETDEWEB)

    Dang, M.; Dupont, J. F.; Jacquemoud, P.; Mylonas, R. [Eidgenoessisches Inst. fuer Reaktorforschung, Wuerenlingen (Switzerland)

    1981-01-15

    The direct coupling of a gas cooled reactor with a closed gas turbine cycle leads to a specific dynamic plant behaviour, which may be summarized as follows: a) any operational transient involving a variation of the core mass flow rate causes a variation of the pressure ratio of the turbomachines and leads unavoidably to pressure and temperature transients in the gas turbine cycle; and b) very severe pressure equalization transients initiated by unlikely events such as the deblading of one or more turbomachines must be taken into account. This behaviour is described and illustrated through results gained from computer analyses performed at the Swiss Federal Institute for Reactor Research (EIR) in Wurenlingen within the scope of the Swiss-German HHT project.

  9. Comprehensive Technical Report, General Electric Direct-Air-Cycle Aircraft Nuclear Propulsion Program, Program Summary and References

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, G.; Rothstein, A.J.

    1962-06-28

    This is one of twenty-one volumes sumarizing the Aircraft Nuclear Propulsion Program of the General Electric Company. This volume discusses the background to the General Electric program, and summarizes the various direct-air-cycle nuclear test assemblies and power plants that were developed. Because of the requirements of high performance, low weight, and small size, vast improvements in existing technology were required to meet the flight objectives. The technological progress achieved during the program is also summarized. The last appendix contains a compilation of the abstracts, tables of contents, and reference lists of the other twenty volumes.

  10. Numerical simulation of a Linear Fresnel Reflector Concentrator used as direct generator in a Solar-GAX cycle

    Energy Technology Data Exchange (ETDEWEB)

    Velazquez, N.; Sauceda, D.; Beltran, R. [Instituto de Ingenieria, Universidad Autonoma de Baja California, Blvd. Benito Juarez y Calle de la Normal s/n, Mexicali, Baja California 21280 (Mexico); Garcia-Valladares, O. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Privada Xochicalco s/n, Temixco, Morelos 62580 (Mexico)

    2010-03-15

    In this work a methodological analysis to design and evaluate the technical feasibility of use a Linear Fresnel Reflector Concentrator (LFRC) as generator in an advanced absorption refrigeration system (Solar-GAX cycle) has been carried out. For this purpose, a detailed one-dimensional numerical simulation of the thermal and fluid-dynamic behavior of a LFRC that solves, in a segregated manner, four subroutines: (a) fluid flow inside the receptor tube, (b) heat transfer in the receptor tube wall, (c) heat transfer in cover tube wall, and (d) solar thermal analysis in the solar concentrator has been developed. The LFRC numerical model has been validated with experimental data obtained from the technical literature; after that, a parametric study for different configurations of design has been carried out in order to obtain the highest solar concentration with the lowest thermal losses, keeping in mind both specific weather conditions and construction restrictions. The numerical result obtained demonstrates that using a LFRC as a direct generator in a Solar-GAX cycle satisfy not only the quantity and quality of the energy demanded by the advanced cooling system, it also allows to obtain higher global efficiencies of the system due to it can be operated in conditions where the maximum performance of the Solar-GAX cycle is obtained without affecting in any significant way the solar collector efficiency. (author)

  11. Numerical simulation of a Linear Fresnel Reflector Concentrator used as direct generator in a Solar-GAX cycle

    International Nuclear Information System (INIS)

    Velazquez, N.; Garcia-Valladares, O.; Sauceda, D.; Beltran, R.

    2010-01-01

    In this work a methodological analysis to design and evaluate the technical feasibility of use a Linear Fresnel Reflector Concentrator (LFRC) as generator in an advanced absorption refrigeration system (Solar-GAX cycle) has been carried out. For this purpose, a detailed one-dimensional numerical simulation of the thermal and fluid-dynamic behavior of a LFRC that solves, in a segregated manner, four subroutines: (a) fluid flow inside the receptor tube, (b) heat transfer in the receptor tube wall, (c) heat transfer in cover tube wall, and (d) solar thermal analysis in the solar concentrator has been developed. The LFRC numerical model has been validated with experimental data obtained from the technical literature; after that, a parametric study for different configurations of design has been carried out in order to obtain the highest solar concentration with the lowest thermal losses, keeping in mind both specific weather conditions and construction restrictions. The numerical result obtained demonstrates that using a LFRC as a direct generator in a Solar-GAX cycle satisfy not only the quantity and quality of the energy demanded by the advanced cooling system, it also allows to obtain higher global efficiencies of the system due to it can be operated in conditions where the maximum performance of the Solar-GAX cycle is obtained without affecting in any significant way the solar collector efficiency.

  12. Biomass Direct Liquefaction Options. TechnoEconomic and Life Cycle Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Tews, Iva J.; Zhu, Yunhua; Drennan, Corinne; Elliott, Douglas C.; Snowden-Swan, Lesley J.; Onarheim, Kristin; Solantausta, Yrjo; Beckman, David

    2014-07-31

    The purpose of this work was to assess the competitiveness of two biomass to transportation fuel processing routes, which were under development in Finland, the U.S. and elsewhere. Concepts included fast pyrolysis (FP), and hydrothermal liquefaction (HTL), both followed by hydrodeoxygenation, and final product refining. This work was carried out as a collaboration between VTT (Finland), and PNNL (USA). The public funding agents for the work were Tekes in Finland and the Bioenergy Technologies Office of the U.S. Department of Energy. The effort was proposed as an update of the earlier comparative technoeconomic assessment performed by the IEA Bioenergy Direct Biomass Liquefaction Task in the 1980s. New developments in HTL and the upgrading of the HTL biocrude product triggered the interest in reinvestigating this comparison of these biomass liquefaction processes. In addition, developments in FP bio-oil upgrading had provided additional definition of this process option, which could provide an interesting comparison.

  13. Effects of Direct Fuel Injection Strategies on Cycle-by-Cycle Variability in a Gasoline Homogeneous Charge Compression Ignition Engine: Sample Entropy Analysis

    Directory of Open Access Journals (Sweden)

    Jacek Hunicz

    2015-01-01

    Full Text Available In this study we summarize and analyze experimental observations of cyclic variability in homogeneous charge compression ignition (HCCI combustion in a single-cylinder gasoline engine. The engine was configured with negative valve overlap (NVO to trap residual gases from prior cycles and thus enable auto-ignition in successive cycles. Correlations were developed between different fuel injection strategies and cycle average combustion and work output profiles. Hypothesized physical mechanisms based on these correlations were then compared with trends in cycle-by-cycle predictability as revealed by sample entropy. The results of these comparisons help to clarify how fuel injection strategy can interact with prior cycle effects to affect combustion stability and so contribute to design control methods for HCCI engines.

  14. Scenario uncertainties in estimating direct land-use change emissions in biomass-to-energy life cycle assessment

    International Nuclear Information System (INIS)

    Curtright, Aimee E.; Johnson, David R.; Willis, Henry H.; Skone, Timothy

    2012-01-01

    The use of biomass for energy production has increasingly been encouraged in the United States, in part motivated by the potential to reduce greenhouse gas (GHG) emissions relative to fossil fuels. However, the GHG-intensity of biomass-derived energy is highly dependent on how the biomass is obtained and used. We explore scenario uncertainty in GHG estimates in the Calculating Uncertainty in Biomass Emissions (CUBE) model and find that direct land-use change emissions that result during the biomass production often dominate the total “farm-to-hopper” GHGs. CUBE represents each land-use change decision as a conversion of land from one of four specified baseline ecosystem to produce one of seven feedstock crops, both distinct by geographic region, and then determines the implied changes in soil organic carbon, root carbon, and above-ground biomass. CUBE therefore synthesizes and organizes the existing literature to represent direct land-use change emissions in a way that can be more readily incorporated into life cycle assessment. Our approach to representing direct land-use change literature has been applied to a specific set of data and offers immediate implications for decisionmakers, but it can also be generalized and replicated in the future, making use of improved scientific data on the magnitude and rates of direct land-use change emissions as it becomes available. -- Highlights: ► The GHG-intensity of bioenergy depends on how the biomass is obtained and used. ► Total GHG emissions may be dominated by direct land-use change emissions. ► There is significant scenario uncertainty in emissions based on the location of production. ► Emissions vary based on time elapsed since land-use change conversions. ► Our approach can be generalized to use improved scientific data in the future.

  15. Operating conditions of an open and direct solar thermal Brayton cycle with optimised cavity receiver and recuperator

    International Nuclear Information System (INIS)

    Le Roux, W.G.; Bello-Ochende, T.; Meyer, J.P.

    2011-01-01

    The small-scale open and direct solar thermal Brayton cycle with recuperator has several advantages, including low cost, low operation and maintenance costs and it is highly recommended. The main disadvantages of this cycle are the pressure losses in the recuperator and receiver, turbomachine efficiencies and recuperator effectiveness, which limit the net power output of such a system. The irreversibilities of the solar thermal Brayton cycle are mainly due to heat transfer across a finite temperature difference and fluid friction. In this paper, thermodynamic optimisation is applied to concentrate on these disadvantages in order to optimise the receiver and recuperator and to maximise the net power output of the system at various steady-state conditions, limited to various constraints. The effects of wind, receiver inclination, rim angle, atmospheric temperature and pressure, recuperator height, solar irradiance and concentration ratio on the optimum geometries and performance were investigated. The dynamic trajectory optimisation method was applied. Operating points of a standard micro-turbine operating at its highest compressor efficiency and a parabolic dish concentrator diameter of 16 m were considered. The optimum geometries, minimum irreversibility rates and maximum receiver surface temperatures of the optimised systems are shown. For an environment with specific conditions and constraints, there exists an optimum receiver and recuperator geometry so that the system produces maximum net power output. -- Highlights: → Optimum geometries exist such that the system produces maximum net power output. → Optimum operating conditions are shown. → Minimum irreversibility rates and minimum entropy generation rates are shown. → Net power output was described in terms of total entropy generation rate. → Effects such as wind, recuperator height and irradiance were investigated.

  16. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling.

    Science.gov (United States)

    Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P; Brownrigg, Alex; Wright, Jonathan P; van Dijk, Niels H; Wagemaker, Marnix

    2015-09-23

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements.

  17. Engineering design of a direct-cycle steam-generating blanket for a long-pulse fusion reactor

    International Nuclear Information System (INIS)

    Cort, G.E.; Hagenson, R.L.; Teasdale, R.W.; Fox, W.E.; Soran, P.D.; Cullingford, H.S.; Bathke, C.G.; Krakowski, R.A.

    1979-01-01

    A comprehensive neutronics, thermohydraulic, and mechanical design of a tritium-breeding blanket for use by a conceptual long-pulse Reversed-Field Pinch Reactor (RFPR) is described. On the basis of constraints imposed by cost and the desire to use existing technology, a direct-cycle steam system and stainless-steel construction were used. For reasons of plasma stability, the RFPR blanket supports a 20-mm-thick copper first wall. Located behind the 1.5-m-radius first wall is a 0.50-m-thick stainless-steel blanket containing a granular bed of Li 2 O through which flows low-pressure helium (0.1 MPa) for tritium extraction. Water/steam tubes radially penetrate this packed bed. The large thermal capacity and low thermal diffusivity of the Li 2 O blanket are sufficient to maintain a nearly constant temperature during the approx. 25-s burn period

  18. Direct-contact condensers for open-cycle OTEC applications: Model validation with fresh water experiments for structured packings

    Energy Technology Data Exchange (ETDEWEB)

    Bharathan, D.; Parsons, B.K.; Althof, J.A.

    1988-10-01

    The objective of the reported work was to develop analytical methods for evaluating the design and performance of advanced high-performance heat exchangers for use in open-cycle thermal energy conversion (OC-OTEC) systems. This report describes the progress made on validating a one-dimensional, steady-state analytical computer of fresh water experiments. The condenser model represents the state of the art in direct-contact heat exchange for condensation for OC-OTEC applications. This is expected to provide a basis for optimizing OC-OTEC plant configurations. Using the model, we examined two condenser geometries, a cocurrent and a countercurrent configuration. This report provides detailed validation results for important condenser parameters for cocurrent and countercurrent flows. Based on the comparisons and uncertainty overlap between the experimental data and predictions, the model is shown to predict critical condenser performance parameters with an uncertainty acceptable for general engineering design and performance evaluations. 33 refs., 69 figs., 38 tabs.

  19. Method of fabricating a catalytic structure

    Science.gov (United States)

    Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

    2009-09-22

    A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

  20. Thermodynamic analysis of a nuclear-hydrogen power system using H2/O2 direct combustion product as a working substance in the bottom cycle

    International Nuclear Information System (INIS)

    Chen, D.Z.; Yu, C.P.

    1990-01-01

    A combined thermodynamic cycle using nuclear and hydrogen energy as heat sources was investigated in this paper. The cycle is composed of top cycle using HTGR as energy source and helium as working medium and a bottom cycle with H 2 /O 2 direct combustion product as working substance. hydrogen and oxygen are thermochemically by splitting of water produced through a part of nuclear heat recovered from the top cycle. They may be delivered to the O 2 /H 2 users or used as fuels for the high temperature bottom Rankine steam cycle. The combined cycle not only uses the new energy sources instead of conventional fossil fuels but it possess the advantages of both helium and steam cycle. It has a high thermal efficiency, large unit capacity, many-sided usage and less pollution. It may represent a new type of combined cycles for future energy conversion and power generation. Using computer diagram, a variety of schemes were calculated and analyzed. The influence of some main parameters upon the cycle performance were also studied

  1. Radiation closure and diurnal cycle of the clear-sky dust instantaneous direct radiative forcing over Arabian Peninsula

    KAUST Repository

    Osipov, Sergey

    2015-04-01

    To better quantify radiative effects of dust over the Arabian Peninsula we have developed a standalone column radiation transport model coupled with the Mie calculations and driven by reanalysis meteorological fields and atmospheric composition. Numerical experiments are carried out for a wide range of aerosol optical depths, including extreme values developed during the dust storm on 18-20 March 2012. Comprehensive ground-based observations and satellite retrievals are used to estimate aerosol optical properties, validate calculations and carry out radiation closure. The broadband surface albedo, fluxes at the bottom and top of the atmosphere as well as instantaneous dust radiative forcing are estimated both from the model and from observations. Diurnal cycle of the the shortwave instantaneous dust direct radiative forcing is studied for a range of aerosol and surface characteristics representative for the Arabian Peninsula. Mechanisms and parameters responsible for diurnal variability of the radiative forcing are evaluated. We found that intrinsic variability of the surface albedo and its dependence on atmospheric conditions along with anisotropic aerosol scattering are mostly responsible for diurnal effects. We also discuss estimates of the climatological dust instantaneous direct radiative forcing over land and the Red Sea using two approaches. The first approach is based on the probability density function of the aerosol optical depth, and the second is based on the climatologically average Spinning Enhanced Visible and Infrared Imager (SEVIRI) aerosol optical depth. Results are compared with Geostationary Earth Radiation Budget (GERB) derived top of the atmosphere climatological forcing over the Red Sea.

  2. Evaluation of technical feasibility of closed-cycle non-equilibrium MHD power generation with direct coal firing. Final report, Task I

    Energy Technology Data Exchange (ETDEWEB)

    1981-11-01

    Program accomplishments in a continuing effort to demonstrate the feasibility of direct coal-fired, closed-cycle MHD power generation are reported. This volume contains the following appendices: (A) user's manual for 2-dimensional MHD generator code (2DEM); (B) performance estimates for a nominal 30 MW argon segmented heater; (C) the feedwater cooled Brayton cycle; (D) application of CCMHD in an industrial cogeneration environment; (E) preliminary design for shell and tube primary heat exchanger; and (F) plant efficiency as a function of output power for open and closed cycle MHD power plants. (WHK)

  3. Effect of working fluids on the performance of a novel direct vapor generation solar organic Rankine cycle system

    International Nuclear Information System (INIS)

    Li, Jing; Alvi, Jahan Zeb; Pei, Gang; Ji, Jie; Li, Pengcheng; Fu, Huide

    2016-01-01

    Highlights: • A novel, flexible direct vapor generation solar ORC is proposed. • Technical feasibility of the system is discussed. • Fluid effect on collector efficiency is explored. • The system is more efficient than solar ORC with HTF. - Abstract: A novel solar organic Rankine cycle (ORC) system with direct vapor generation (DVG) is proposed. A heat storage unit is embedded in the ORC to guarantee the stability of power generation. Compared with conventional solar ORCs, the proposed system avoids the secondary heat transfer intermediate and shows good reaction to the fluctuation of solar radiation. The technical feasibility of the system is discussed. Performance is analyzed by using 17 dry and isentropic working fluids. Fluid effects on the efficiencies of ORC, collectors and the whole system are studied. The results indicate that the collector efficiency generally decreases while the ORC and system efficiencies increase with the increment in fluid critical temperature. At evaporation temperature of 120 °C and solar radiation of 800 Wm −2 , the ORC, collector and overall thermal efficiencies of R236fa are 10.59, 56.14 and 5.08% while their values for Benzene are 12.5, 52.58 and 6.57% respectively. The difference between collector efficiencies using R236fa and Benzene gets larger at lower solar radiation. The heat collection is strongly correlated with latent and sensible heat of the working fluid. Among the fluids, R123 exhibits the highest overall performance and seems to be suitable for the proposed system in the short term.

  4. Helium heater design for the helium direct cycle component test facility. [for gas-cooled nuclear reactor power plant

    Science.gov (United States)

    Larson, V. R.; Gunn, S. V.; Lee, J. C.

    1975-01-01

    The paper describes a helium heater to be used to conduct non-nuclear demonstration tests of the complete power conversion loop for a direct-cycle gas-cooled nuclear reactor power plant. Requirements for the heater include: heating the helium to a 1500 F temperature, operating at a 1000 psia helium pressure, providing a thermal response capability and helium volume similar to that of the nuclear reactor, and a total heater system helium pressure drop of not more than 15 psi. The unique compact heater system design proposed consists of 18 heater modules; air preheaters, compressors, and compressor drive systems; an integral control system; piping; and auxiliary equipment. The heater modules incorporate the dual-concentric-tube 'Variflux' heat exchanger design which provides a controlled heat flux along the entire length of the tube element. The heater design as proposed will meet all system requirements. The heater uses pressurized combustion (50 psia) to provide intensive heat transfer, and to minimize furnace volume and heat storage mass.

  5. Economic Analysis on Direct Use of Spent Pressurized Water Reactor Fuel in CANDU Reactors - IV: DUPIC Fuel Cycle Cost

    International Nuclear Information System (INIS)

    Ko, Won Il; Choi, Hangbok; Yang, Myung Seung

    2001-01-01

    This study examines the economics of the DUPIC fuel cycle using unit costs of fuel cycle components estimated based on conceptual designs. The fuel cycle cost (FCC) was calculated by a deterministic method in which reference values of fuel cycle components are used. The FCC was then analyzed by a Monte Carlo simulation to get the uncertainty of the FCC associated with the unit costs of the fuel cycle components. From the deterministic analysis on the equilibrium fuel cycle model, the DUPIC FCC was estimated to be 6.21 to 6.34 mills/kW.h for DUPIC fuel options, which is a little smaller than that of the once-through FCC by 0.07 to 0.27 mills/kW.h. Considering the uncertainty (0.40 to 0.44 mills/kW.h) of the FCC estimated by the Monte Carlo simulation method, the cost difference between the DUPIC and once-through fuel cycle is negligible. On the other hand, the material balance calculation has shown that the DUPIC fuel cycle can save natural uranium resources by ∼20% and reduce the spent fuel arising by ∼65% compared with the once-through fuel cycle. In conclusion, the DUPIC fuel cycle is comparable with the once-through fuel cycle from the viewpoint of FCC. In the future, it should be important to consider factors such as the environmental benefit owing to natural uranium savings, the capability of reusing spent pressurized water reactor fuel, and the safeguardability of the fuel cycle when deciding on an advanced nuclear fuel cycle option

  6. Carbon Footprint of Inbound Tourism to Iceland: A Consumption-Based Life-Cycle Assessment including Direct and Indirect Emissions

    Directory of Open Access Journals (Sweden)

    Hannah Sharp

    2016-11-01

    Full Text Available The greenhouse gas (GHG emissions caused by tourism have been studied from several perspectives, but few studies exist that include all direct and indirect emissions, particularly those from aviation. In this study, an input/output-based hybrid life-cycle assessment (LCA method is developed to assess the consumption-based carbon footprint of the average tourist including direct and indirect emissions. The total inbound tourism-related GHG emissions are also calculated within a certain region. As a demonstration of the method, the full carbon footprint of an average tourist is assessed as well as the total GHG emissions induced by tourism to Iceland over the period of 2010–2015, with the presented approach applicable in other contexts as well. Iceland provides an interesting case due to three features: (1 the tourism sector in Iceland is the fastest-growing industry in the country with an annual growth rate of over 20% over the past five years; (2 almost all tourists arrive by air; and (3 the country has an almost emissions-free energy industry and an import-dominated economy, which emphasise the role of the indirect emissions. According to the assessment, the carbon footprint for the average tourist is 1.35 tons of CO2-eq, but ranges from 1.1 to 3.2 tons of CO2-eq depending on the distance travelled by air. Furthermore, this footprint is increasing due to the rise in average flight distances travelled to reach the country. The total GHG emissions caused by tourism in Iceland have tripled from approximately 600,000 tons of CO2-eq in 2010 to 1,800,000 tons in 2015. Aviation accounts for 50%–82% of this impact (depending on the flight distance underlining the importance of air travel, especially as tourism-related aviation is forecasted to grow significantly in the near future. From a method perspective, the carbon footprinting application presented in the study would seem to provide an efficient way to study both the direct and indirect

  7. On the Structural Context and Identification of Enzyme Catalytic Residues

    Directory of Open Access Journals (Sweden)

    Yu-Tung Chien

    2013-01-01

    Full Text Available Enzymes play important roles in most of the biological processes. Although only a small fraction of residues are directly involved in catalytic reactions, these catalytic residues are the most crucial parts in enzymes. The study of the fundamental and unique features of catalytic residues benefits the understanding of enzyme functions and catalytic mechanisms. In this work, we analyze the structural context of catalytic residues based on theoretical and experimental structure flexibility. The results show that catalytic residues have distinct structural features and context. Their neighboring residues, whether sequence or structure neighbors within specific range, are usually structurally more rigid than those of noncatalytic residues. The structural context feature is combined with support vector machine to identify catalytic residues from enzyme structure. The prediction results are better or comparable to those of recent structure-based prediction methods.

  8. Catalytic combustion of gasified waste - Experimental part. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Jaeraas, Sven; Kusar, Henrik [Royal Institute of Technology, Stockholm (Sweden). Chemical Engineering and Technology

    2003-08-01

    This final report covers the work that has been performed within the project P 10547-2, 'Catalytic combustion of gasified waste - system analysis ORWARE'. This project is part of the research programme 'Energy from Waste' financed by the Swedish National Energy Administration. The project has been carried out at the division of Industrial Ecology and at the division of Chemical Technology at Royal Inst. of Technology. The aim of the project has been to study the potentials for catalytic combustion of gasified waste. The supposed end user of the technique is a smaller community in Sweden with 15,000-20,000 inhabitants. The project contains of two sub projects: an experimental part carried out at Chemical Technology and a system analysis carried out at Industrial Ecology. This report covers the experimental part of the project carried out at Chemical Technology. The aim for the experimental part has been to develop and test catalysts with long life-time and a high performance, to reduce the thermal-NO{sub x} below 5 ppm and to significantly reduce NO{sub x} formed from fuel-bound nitrogen. Different experimental studies have been carried out within the project: a set-up of catalytic materials have been tested over a synthetic mixture of the gasified waste, the influence of sulfur present in the gas stream, NO{sub x} formation from fuel bound nitrogen, kinetic studies of CO and H{sub 2} with and without the presence of water and the effects of adding a co-metal to palladium catalysts Furthermore a novel annular reactor design has been used to carry out experiments for kinetic measurements. Real gasification tests of waste pellets directly coupled to catalytic combustion have successfully been performed. The results obtained from the experiments, both the catalytic combustion and from the gasification, have been possible to use in the system analysis. The aim of the system analysis of catalytic combustion of gasified waste takes into consideration

  9. Direct determination of tellurium and its redox speciation at the low nanogram level in natural waters by catalytic cathodic stripping voltammetry.

    Science.gov (United States)

    Biver, Marc; Quentel, François; Filella, Montserrat

    2015-11-01

    Tellurium is one of the elements recently identified as technologically critical and is becoming a new emergent contaminant. No reliable method exists for its determination in environmental samples such as natural waters. This gap is filled by the method described here; it allows the rapid detection of trace concentrations of Te(IV) and Te(VI) in surface waters by differential pulse cathodic stripping voltammetry. It is based on the proton reduction catalysed by the absorption of Te(IV) on the mercury electrode. Under our conditions (0.1 mol L(-1) HCl) a detection limit of about 5 ng L(-1) for a deposition time of 300 s is achieved. Organic matter does not represent a problem at low concentrations; higher concentrations are eliminated by adsorptive purification. Tellurium occurs primarily as Te(IV) and Te(VI) in natural waters. Thus, determining total Te requires the reduction of Te(VI) that it is not electroactive. A number of reduction procedures have been carefully evaluated and a method based on the addition of TiCl3 to the acidified samples has been proven to reduce Te(VI) at the trace level to Te(IV) reliably and quantitatively. Therefore, the procedure described allows the direct determination of total Te and its redox speciation. It is flexible, reliable and cost effective compared to any possible alternative method based on the common preconcentration-ICPMS approach. It is readily implementable as a routine method and can be deployed in the field with relative ease. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. SHORT COMMUNICATION CATALYTIC KINETIC ...

    African Journals Online (AJOL)

    IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

  11. Catalytic distillation process

    Science.gov (United States)

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  12. Catalytic distillation structure

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  13. Performance of an Otto cycle motor with natural gas direct injection; Desempenho de um motor ciclo Otto com injecao direta de gas natural

    Energy Technology Data Exchange (ETDEWEB)

    Barbosa, Cleiton Rubens Formiga

    1997-07-01

    A Otto cycle engine with natural gas direct injection, during the inlet stroke, was submitted to runs with full power in a Foucaut dynamometer. The results obtained show a increase in the volumetric efficiency of the engine with natural gas direct injection when compared with natural gas injection applied in the inlet manifold, upstream of the throttle butterfly. In the conversion to natural gas direct injection, the technical characteristics were not changed. A kit for natural gas direct injection, with electronic management was located on the cylinder head of the test engine. Maintaining the pressure constant in the natural gas fuel line, using a reduction valve, the mass of fuel injected into the cylinder was regulated, varying the opening time of the solenoid valve fuel injector. Engine performance data is compared, emphasizing the factors that contribute to this increase in relative volumetric efficiency. Modifications are made to maximize the power of the engine with natural gas direct injection. (author)

  14. Equilibrium core layout for the 1000 MW direct cycle HTR (HHT) with hexagonal monolith moulded fuel blocks

    Energy Technology Data Exchange (ETDEWEB)

    Dworak, A

    1973-03-15

    The aim of this survey is to calculate an equilibrium Thorium fuel cycle for a 1000 MW HHT-core in off-load refuelling with hexagonal monolith moulded fuel blocks. It was tried to achieve an axial power distribution similar to the advanced pebble-bed reactors (OTTO) by introducing three axial core zones with different heavy metal content and initial enrichment.

  15. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

    NARCIS (Netherlands)

    Zhang, X.; Van Hulzen, M.; Singh, D.P.; Brownrigg, A.W.; Wright, J.P.; Van Dijk, N.H.; Wagemaker, M.

    2015-01-01

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is

  16. Corrigendum to "Sinusoidal potential cycling operation of a direct ethanol fuel cell to improving carbon dioxide yields" [J. Power Sources 268 (5 December 2014) 439-442

    Science.gov (United States)

    Majidi, Pasha; Pickup, Peter G.

    2016-09-01

    The authors regret that Equation (5) is incorrect and has resulted in errors in Fig. 4 and the efficiencies stated on p. 442. The corrected equation, figure and text are presented below. In addition, the title should be 'Sinusoidal potential cycling operation of a direct ethanol fuel cell to improve carbon dioxide yields', and the reversible cell potential quoted on p. 441 should be 1.14 V. The authors would like to apologise for any inconvenience caused.

  17. Catalytic nanoporous membranes

    Science.gov (United States)

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  18. Toward Facilitative Mentoring and Catalytic Interventions

    Science.gov (United States)

    Smith, Melissa K.; Lewis, Marilyn

    2015-01-01

    In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

  19. Direct comparasion of an engine working under Otto, Miller end Diesel cycles : thermodynamic analysis and real engine performance

    OpenAIRE

    Ribeiro, Bernardo Sousa; Martins, Jorge

    2007-01-01

    One of the ways to improve thermodynamic efficiency of Spark Ignition engines is by the optimisation of valve timing and lift and compression ratio. The throttleless engine and the Miller cycle engine are proven concepts for efficiency improvements of such engines. This paper reports on an engine with variable valve timing (VVT) and variable compression ratio (VCR) in order to fulfill such an enhancement of efficiency. Engine load is controlled by the valve opening per...

  20. Catalytic Wastewater Treatment Using Pillared Clays

    Science.gov (United States)

    Perathoner, Siglinda; Centi, Gabriele

    After introduction on the use of solid catalysts in wastewater treatment technologies, particularly advanced oxidation processes (AOPs), this review discussed the use of pillared clay (PILC) materials in three applications: (i) wet air catalytic oxidation (WACO), (ii) wet hydrogen peroxide catalytic oxidation (WHPCO) on Cu-PILC and Fe-PILC, and (iii) behavior of Ti-PILC and Fe-PILC in the photocatalytic or photo-Fenton conversion of pollutants. Literature data are critically analyzed to evidence the main direction to further investigate, in particularly with reference to the possible practical application of these technologies to treat industrial, municipal, or agro-food production wastewater.

  1. Investigating the Dendritic Growth during Full Cell Cycling of Garnet Electrolyte in Direct Contact with Li Metal.

    Science.gov (United States)

    Aguesse, Frederic; Manalastas, William; Buannic, Lucienne; Lopez Del Amo, Juan Miguel; Singh, Gurpreet; Llordés, Anna; Kilner, John

    2017-02-01

    All-solid-state batteries including a garnet ceramic as electrolyte are potential candidates to replace the currently used Li-ion technology, as they offer safer operation and higher energy storage performances. However, the development of ceramic electrolyte batteries faces several challenges at the electrode/electrolyte interfaces, which need to withstand high current densities to enable competing C-rates. In this work, we investigate the limits of the anode/electrolyte interface in a full cell that includes a Li-metal anode, LiFePO 4 cathode, and garnet ceramic electrolyte. The addition of a liquid interfacial layer between the cathode and the ceramic electrolyte is found to be a prerequisite to achieve low interfacial resistance and to enable full use of the active material contained in the porous electrode. Reproducible and constant discharge capacities are extracted from the cathode active material during the first 20 cycles, revealing high efficiency of the garnet as electrolyte and the interfaces, but prolonged cycling leads to abrupt cell failure. By using a combination of structural and chemical characterization techniques, such as SEM and solid-state NMR, as well as electrochemical and impedance spectroscopy, it is demonstrated that a sudden impedance drop occurs in the cell due to the formation of metallic Li and its propagation within the ceramic electrolyte. This degradation process is originated at the interface between the Li-metal anode and the ceramic electrolyte layer and leads to electromechanical failure and cell short-circuit. Improvement of the performances is observed when cycling the full cell at 55 °C, as the Li-metal softening favors the interfacial contact. Various degradation mechanisms are proposed to explain this behavior.

  2. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    -ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

  3. The direct-stress fatigue strength of 17S-T aluminum alloy throughout the range from 1/2 to 500,000,000 cycles of stress

    Science.gov (United States)

    Hartmann, E C; Stickley, G W

    1942-01-01

    Fatigue-test were conducted on six specimens made from 3/4-inch-diameter 17S-T rolled-and-drawn rod for the purpose of obtaining additional data on the fatigue life of the material at stresses up to the static strength. The specimens were tested in direct tension using a stress range from zero to a maximum in tension. A static testing machine was used to apply repeated loads in the case of the first three specimens; the other three specimens were tested in a direct tension-compression fatigue machine. The direct-stress fatigue curve obtained for the material indicates that, in the range of stresses above about two-thirds the tensile strength, the fatigue strength is higher than might be expected by simply extrapolating the ordinary curve of stress plotted against the number of cycles determined at lower stresses.

  4. Catalytic pyrolysis of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Vail' eva, N A; Buyanov, R A

    1979-01-01

    Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

  5. Catalytic Conversion of Biofuels

    DEFF Research Database (Denmark)

    Jørgensen, Betina

    This thesis describes the catalytic conversion of bioethanol into higher value chemicals. The motivation has been the unavoidable coming depletion of the fossil resources. The thesis is focused on two ways of utilising ethanol; the steam reforming of ethanol to form hydrogen and the partial oxida...

  6. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  7. Catalytic methanol dissociation

    International Nuclear Information System (INIS)

    Alcinikov, Y.; Fainberg, V.; Garbar, A.; Gutman, M.; Hetsroni, G.; Shindler, Y.; Tatrtakovsky, L.; Zvirin, Y.

    1998-01-01

    Results of the methanol dissociation study on copper/potassium catalyst with alumina support at various temperatures are presented. The following gaseous and liquid products at. The catalytic methanol dissociation is obtained: hydrogen, carbon monoxide, carbon dioxide, methane, and dimethyl ether. Formation rates of these products are discussed. Activation energies of corresponding reactions are calculated

  8. Back-end of the nuclear fuel cycle. A comparison of the direct disposal and reprocessing options

    International Nuclear Information System (INIS)

    Allan, C.J.; Baumgartner, P.

    1997-01-01

    Based on the need to address public concerns, the need to ensure long-term safety and an ethical concern for future generations, many countries are developing technology to dispose of nuclear fuel waste. The waste substances in used fuel can be disposed of either by directly disposing of the used fuel assemblies themselves, or by disposing of the long-lived waste from fuel reprocessing. The basic thesis of this paper is that the direct disposal of either used fuel or of the long-lived heat-generating and non-heat generating waste that arise from reprocessing is technically and economically feasible and that both options will meet the fundamental objectives of protecting human health and the environment. Decisions about whether, or when, to reprocess used fuel, or about whether to dispose of used fuel directly, are not fundamentally waste management issues. (author)

  9. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  10. Optimum performance of the small scale open and direct solar thermal Brayton cycle at various environmental conditions and constraints

    Energy Technology Data Exchange (ETDEWEB)

    Le Roux, W.G.; Bello-Ochende, T.; Meyer, J.P. [Department of Mechanical and Aeronautical Engineering, University of Pretoria, (South Africa)

    2011-07-01

    The energy of the sun can be transformed into mechanical power through the use of concentrated solar power systems. The use of the Brayton cycle with recuperator has significant advantages but also raises issues such as pressure loss and low net power output which are mainly due to irreversibilities of heat transfer and fluid friction. The aim of this study is to optimize the system to generate maximum net power output. Thermodynamic and dynamic trajectory optimizations were performed on a dish concentrator and an off-the-shelf micro-turbine and the effects of wind, solar irradiance and other environmental conditions and constraints on the power output were analyzed. Results showed that the maximum power output is increased when wind decreases and irradiance increases; solar irradiance was found to have a more significant impact than wind. This study highlighted the factors which impact the power generation of concentrated solar power systems so that designers can take them into account.

  11. Effect of Drive Cycle and Gasoline Particulate Filter on the Size and Morphology of Soot Particles Emitted from a Gasoline-Direct-Injection Vehicle.

    Science.gov (United States)

    Saffaripour, Meghdad; Chan, Tak W; Liu, Fengshan; Thomson, Kevin A; Smallwood, Gregory J; Kubsh, Joseph; Brezny, Rasto

    2015-10-06

    The size and morphology of particulate matter emitted from a light-duty gasoline-direct-injection (GDI) vehicle, over the FTP-75 and US06 transient drive cycles, have been characterized by transmission-electron-microscope (TEM) image analysis. To investigate the impact of gasoline particulate filters on particulate-matter emission, the results for the stock-GDI vehicle, that is, the vehicle in its original configuration, have been compared to the results for the same vehicle equipped with a catalyzed gasoline particulate filter (GPF). The stock-GDI vehicle emits graphitized fractal-like aggregates over all driving conditions. The mean projected area-equivalent diameter of these aggregates is in the 78.4-88.4 nm range and the mean diameter of primary particles varies between 24.6 and 26.6 nm. Post-GPF particles emitted over the US06 cycle appear to have an amorphous structure, and a large number of nucleation-mode particles, depicted as low-contrast ultrafine droplets, are observed in TEM images. This indicates the emission of a substantial amount of semivolatile material during the US06 cycle, most likely generated by the incomplete combustion of accumulated soot in the GPF during regeneration. The size of primary particles and soot aggregates does not vary significantly by implementing the GPF over the FTP-75 cycle; however, particles emitted by the GPF-equipped vehicle over the US06 cycle are about 20% larger than those emitted by the stock-GDI vehicle. This may be attributed to condensation of large amounts of organic material on soot aggregates. High-contrast spots, most likely solid nonvolatile cores, are observed within many of the nucleation-mode particles emitted over the US06 cycle by the GPF-equipped vehicle. These cores are either generated inside the engine or depict incipient soot particles which are partially carbonized in the exhaust line. The effect of drive cycle and the GPF on the fractal parameters of particles, such as fractal dimension and

  12. Open-cycle magnetohydrodynamic power plant based upon direct-contact closed-loop high-temperature heat exchanger

    Science.gov (United States)

    Berry, G.F.; Minkov, V.; Petrick, M.

    1981-11-02

    A magnetohydrodynamic (MHD) power generating system is described in which ionized combustion gases with slag and seed are discharged from an MHD combustor and pressurized high temperature inlet air is introduced into the combustor for supporting fuel combustion at high temperatures necessary to ionize the combustion gases, and including a heat exchanger in the form of a continuous loop with a circulating heat transfer liquid such as copper oxide. The heat exchanger has an upper horizontal channel for providing direct contact between the heat transfer liquid and the combustion gases to cool the gases and condense the slag which thereupon floats on the heat transfer liquid and can be removed from the channel, and a lower horizontal channel for providing direct contact between the heat transfer liquid and pressurized air for preheating the inlet air. The system further includes a seed separator downstream of the heat exchanger.

  13. Concentric catalytic combustor

    Science.gov (United States)

    Bruck, Gerald J [Oviedo, FL; Laster, Walter R [Oviedo, FL

    2009-03-24

    A catalytic combustor (28) includes a tubular pressure boundary element (90) having a longitudinal flow axis (e.g., 56) separating a first portion (94) of a first fluid flow (e.g., 24) from a second portion (95) of the first fluid flow. The pressure boundary element includes a wall (96) having a plurality of separate longitudinally oriented flow paths (98) annularly disposed within the wall and conducting respective portions (100, 101) of a second fluid flow (e.g., 26) therethrough. A catalytic material (32) is disposed on a surface (e.g., 102, 103) of the pressure boundary element exposed to at least one of the first and second portions of the first fluid flow.

  14. Catalytic exhaust control

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H

    1973-09-01

    Recent achievements and problems in the development of exhaust control devices in the USA are reviewed. To meet the 1976 emission standards, catalytic systems for the oxidation of carbon monoxide and hydrocarbons and for the reduction of nitrogen oxides to nitrogen and water are needed. While oxidizing catalysts using platinum, palladium, copper, vanadium, and chromium appplied on alumina or ceramic materials are more or less effective in emission control, there are no catalytic devices for the reduction of nitrogen oxides with the required useful life of 25,000 to 50,000 miles as yet available. In the case of platinum catalysts on monolithic supports, the operating temperature of 650 to 750/sup 0/C as required for the oxidation process may cause inactivation of the catalysts and fusion of the support material. The oxidation of CO and hydrocarbons is inhibited by high concentrations of CO, nitric oxide, and hydrocarbons. The use of catalytic converters requires the use of lead-free or low-lead gasoline. The nitrogen oxides conversion efficiency is considerably influenced by the oxygen-to-CO ratio of the exhaust gas, which makes limitation of this ratio necessary.

  15. Direct and indirect costs of dinitrogen fixation in Crocosphaera watsonii WH8501 and possible implications for the nitrogen cycle

    Directory of Open Access Journals (Sweden)

    Tobias eGroßkopf

    2012-07-01

    Full Text Available The recent detection of heterotrophic nitrogen (N2 fixation in deep waters of the southern Californian and Peruvian OMZ questions our current understanding of marine N2 fixation as a process confined to oligotrophic surface waters of the oceans. In experiments with Crocosphaera watsonii WH8501, a marine unicellular diazotrophic (N2-fixing cyanobacterium, we demonstrated that the presence of high nitrate concentrations (up to 800 µM had no inhibitory effect on growth and N2 fixation over a period of two weeks. In contrast, the environmental oxygen concentration significantly influenced rates of N2 fixation and respiration, as well as carbon and nitrogen cellular content of C. watsonii over a 24 hour period. Cells grown under lowered oxygen atmosphere (5% had a higher nitrogenase activity and respired less carbon during the dark cycle than under normal oxygen atmosphere (20%. Respiratory oxygen drawdown during the dark period could be fully explained (104% by energetic needs due to basal metabolism and N2 fixation at low oxygen, while at normal oxygen these two processes could only account for 40% of the measured respiration rate. Our results revealed that under normal oxygen concentration most of the energetic costs during N2 fixation (~60% are not derived from the process of N2 fixation per se but rather from the indirect costs incurred for the removal of intracellular oxygen or by the reversal of oxidative damage (e.g. nitrogenase de novo synthesis. Theoretical calculations suggest a slight energetic advantage of N2 fixation relative to assimilatory nitrate uptake for heterotrophic and phototrophic growth, when oxygen supply is in balance with the oxygen requirement for cellular respiration (i.e. energy generation for basal metabolism and N2 fixation. Taken together our results imply the existence of a niche for diazotrophic organisms inside oxygen minimum zones, which are predicted to further expand in the future ocean.

  16. Manipulation of cell cycle progression can counteract the apparent loss of correction frequency following oligonucleotide-directed gene repair

    Directory of Open Access Journals (Sweden)

    Kmiec Eric B

    2007-02-01

    Full Text Available Abstract Background Single-stranded oligonucleotides (ssODN are used routinely to direct specific base alterations within mammalian genomes that result in the restoration of a functional gene. Despite success with the technique, recent studies have revealed that following repair events, correction frequencies decrease as a function of time, possibly due to a sustained activation of damage response signals in corrected cells that lead to a selective stalling. In this study, we use thymidine to slow down the replication rate to enhance repair frequency and to maintain substantial levels of correction over time. Results First, we utilized thymidine to arrest cells in G1 and released the cells into S phase, at which point specific ssODNs direct the highest level of correction. Next, we devised a protocol in which cells are maintained in thymidine following the repair reaction, in which the replication is slowed in both corrected and non-corrected cells and the initial correction frequency is retained. We also present evidence that cells enter a senescence state upon prolonged treatment with thymidine but this passage can be avoided by removing thymidine at 48 hours. Conclusion Taken together, we believe that thymidine may be used in a therapeutic fashion to enable the maintenance of high levels of treated cells bearing repaired genes.

  17. A Life Cycle Assessment Case Study of Coal-Fired Electricity Generation with Humidity Swing Direct Air Capture of CO2 versus MEA-Based Postcombustion Capture.

    Science.gov (United States)

    van der Giesen, Coen; Meinrenken, Christoph J; Kleijn, René; Sprecher, Benjamin; Lackner, Klaus S; Kramer, Gert Jan

    2017-01-17

    Most carbon capture and storage (CCS) envisions capturing CO 2 from flue gas. Direct air capture (DAC) of CO 2 has hitherto been deemed unviable because of the higher energy associated with capture at low atmospheric concentrations. We present a Life Cycle Assessment of coal-fired electricity generation that compares monoethanolamine (MEA)-based postcombustion capture (PCC) of CO 2 with distributed, humidity-swing-based direct air capture (HS-DAC). Given suitable temperature, humidity, wind, and water availability, HS-DAC can be largely passive. Comparing energy requirements of HS-DAC and MEA-PCC, we find that the parasitic load of HS-DAC is less than twice that of MEA-PCC (60-72 kJ/mol versus 33-46 kJ/mol, respectively). We also compare other environmental impacts as a function of net greenhouse gas (GHG) mitigation: To achieve the same 73% mitigation as MEA-PCC, HS-DAC would increase nine other environmental impacts by on average 38%, whereas MEA-PCC would increase them by 31%. Powering distributed HS-DAC with photovoltaics (instead of coal) while including recapture of all background GHG, reduces this increase to 18%, hypothetically enabling coal-based electricity with net-zero life-cycle GHG. We conclude that, in suitable geographies, HS-DAC can complement MEA-PCC to enable CO 2 capture independent of time and location of emissions and recapture background GHG from fossil-based electricity beyond flue stack emissions.

  18. Milestone Report #2: Direct Evaporator Leak and Flammability Analysis Modifications and Optimization of the Organic Rankine Cycle to Improve the Recovery of Waste Heat

    Energy Technology Data Exchange (ETDEWEB)

    Guillen, Donna Post [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2013-09-01

    The direct evaporator is a simplified heat exchange system for an Organic Rankine Cycle (ORC) that generates electricity from a gas turbine exhaust stream. Typically, the heat of the exhaust stream is transferred indirectly to the ORC by means of an intermediate thermal oil loop. In this project, the goal is to design a direct evaporator where the working fluid is evaporated in the exhaust gas heat exchanger. By eliminating one of the heat exchangers and the intermediate oil loop, the overall ORC system cost can be reduced by approximately 15%. However, placing a heat exchanger operating with a flammable hydrocarbon working fluid directly in the hot exhaust gas stream presents potential safety risks. The purpose of the analyses presented in this report is to assess the flammability of the selected working fluid in the hot exhaust gas stream stemming from a potential leak in the evaporator. Ignition delay time for cyclopentane at temperatures and pressure corresponding to direct evaporator operation was obtained for several equivalence ratios. Results of a computational fluid dynamic analysis of a pinhole leak scenario are given.

  19. Mutations in the catalytic core or the C-terminus of murine leukemia virus (MLV) integrase disrupt virion infectivity and exert diverse effects on reverse transcription

    International Nuclear Information System (INIS)

    Steinrigl, Adolf; Nosek, Dagmara; Ertl, Reinhard; Guenzburg, Walter H.; Salmons, Brian; Klein, Dieter

    2007-01-01

    Understanding of the structures and functions of the retroviral integrase (IN), a key enzyme in the viral replication cycle, is essential for developing antiretroviral treatments and facilitating the development of safer gene therapy vehicles. Thus, four MLV IN-mutants were constructed in the context of a retroviral vector system, harbouring either a substitution in the catalytic centre, deletions in the C-terminus, or combinations of both modifications. IN-mutants were tested for their performance in different stages of the viral replication cycle: RNA-packaging; RT-activity; transient and stable infection efficiency; dynamics of reverse transcription and nuclear entry. All mutant vectors packaged viral RNA with wild-type efficiencies and displayed only slight reductions in RT-activity. Deletion of either the IN C-terminus alone, or in addition to part of the catalytic domain exerted contrasting effects on intracellular viral DNA levels, implying that IN influences reverse transcription in more than one direction

  20. On the influence of cloud fraction diurnal cycle and sub-grid cloud optical thickness variability on all-sky direct aerosol radiative forcing

    International Nuclear Information System (INIS)

    Min, Min; Zhang, Zhibo

    2014-01-01

    The objective of this study is to understand how cloud fraction diurnal cycle and sub-grid cloud optical thickness variability influence the all-sky direct aerosol radiative forcing (DARF). We focus on the southeast Atlantic region where transported smoke is often observed above low-level water clouds during burning seasons. We use the CALIOP observations to derive the optical properties of aerosols. We developed two diurnal cloud fraction variation models. One is based on sinusoidal fitting of MODIS observations from Terra and Aqua satellites. The other is based on high-temporal frequency diurnal cloud fraction observations from SEVIRI on board of geostationary satellite. Both models indicate a strong cloud fraction diurnal cycle over the southeast Atlantic region. Sensitivity studies indicate that using a constant cloud fraction corresponding to Aqua local equatorial crossing time (1:30 PM) generally leads to an underestimated (less positive) diurnal mean DARF even if solar diurnal variation is considered. Using cloud fraction corresponding to Terra local equatorial crossing time (10:30 AM) generally leads overestimation. The biases are a typically around 10–20%, but up to more than 50%. The influence of sub-grid cloud optical thickness variability on DARF is studied utilizing the cloud optical thickness histogram available in MODIS Level-3 daily data. Similar to previous studies, we found the above-cloud smoke in the southeast Atlantic region has a strong warming effect at the top of the atmosphere. However, because of the plane-parallel albedo bias the warming effect of above-cloud smoke could be significantly overestimated if the grid-mean, instead of the full histogram, of cloud optical thickness is used in the computation. This bias generally increases with increasing above-cloud aerosol optical thickness and sub-grid cloud optical thickness inhomogeneity. Our results suggest that the cloud diurnal cycle and sub-grid cloud variability are important factors

  1. Ignition assist systems for direct-injected, diesel cycle, medium-duty alternative fuel engines: Final report phase 1

    Energy Technology Data Exchange (ETDEWEB)

    Chan, A.K.

    2000-02-23

    This report is a summary of the results of Phase 1 of this contract. The objective was to evaluate the potential of assist technologies for direct-injected alternative fuel engines vs. glow plug ignition assist. The goal was to demonstrate the feasibility of an ignition system life of 10,000 hours and a system cost of less than 50% of the glow plug system, while meeting or exceeding the engine thermal efficiency obtained with the glow plug system. There were three tasks in Phase 1. Under Task 1, a comprehensive review of feasible ignition options for DING engines was completed. The most promising options are: (1) AC and the ''SmartFire'' spark, which are both long-duration, low-power (LDLP) spark systems; (2) the short-duration, high-power (SDHP) spark system; (3) the micropilot injection ignition; and (4) the stratified charge plasma ignition. Efforts concentrated on investigating the AC spark, SmartFire spark, and short-duration/high-power spark systems. Using proprietary pricing information, the authors predicted that the commercial costs for the AC spark, the short-duration/high-power spark and SmartFire spark systems will be comparable (if not less) to the glow plug system. Task 2 involved designing and performing bench tests to determine the criteria for the ignition system and the prototype spark plug for Task 3. The two most important design criteria are the high voltage output requirement of the ignition system and the minimum electrical insulation requirement for the spark plug. Under Task 3, all the necessary hardware for the one-cylinder engine test was designed. The hardware includes modified 3126 cylinder heads, specially designed prototype spark plugs, ignition system electronics, and parts for the system installation. Two 3126 cylinder heads and the SmartFire ignition system were procured, and testing will begin in Phase 2 of this subcontract.

  2. Catalytic biomass pyrolysis process

    Science.gov (United States)

    Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.; Kataria, Atish; Shen, Jian-Ping

    2018-04-17

    Described herein are processes for converting a biomass starting material (such as lignocellulosic materials) into a low oxygen containing, stable liquid intermediate that can be refined to make liquid hydrocarbon fuels. More specifically, the process can be a catalytic biomass pyrolysis process wherein an oxygen removing catalyst is employed in the reactor while the biomass is subjected to pyrolysis conditions. The stream exiting the pyrolysis reactor comprises bio-oil having a low oxygen content, and such stream may be subjected to further steps, such as separation and/or condensation to isolate the bio-oil.

  3. Catalytic reforming methods

    Science.gov (United States)

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  4. Influence of dipping cycles on physical, optical, and electrical properties of Cu 2 NiSnS 4 : Direct solution dip coating for photovoltaic applications

    Energy Technology Data Exchange (ETDEWEB)

    Mokurala, Krishnaiah; Mallick, Sudhanshu; Bhargava, Parag; Siol, Sebastian; Klein, Talysa R.; van Hest, Maikel F. A. M.

    2017-11-01

    Direct solution coating technique has emerged as a promising economically viable process for earth abundant chalcogenide absorber materials for photovoltaic applications. Here, direct ethanol based dip coating of earth abundant Cu2NiSnS4 (CNTS) films on soda lime glass (SLG), molybdenum coated glass (Mo), and fluorine doped tin oxide coated glass (FTO) substrates is investigated. The structural and morphological properties of pre-annealed and sulfurized CNTS films coated on SLG, FTO, and Mo substrates are reported. The influence of dipping cycles on composition and optoelectronic properties of pre-annealed and sulfurized CNTS films deposited on SLG substrate is presented. Energy dispersive spectroscopy (EDS) and X-ray fluorescence (XRF) analysis reveal how changes in thickness and elemental composition affect morphology and optoelectronic properties. The obtained absorption coefficient, optical bandgap, resistivity and mobility of pre - annealed and sulfurized films are found to be 104 cm-1, 1.5 eV, 0.48 Ocm, 3.4 cm2/Vs and 104 cm-1, 1.29 eV, 0.14 Ocm, 11.0 cm2/Vs, respectively. These properties are well suited for photovoltaic applications and lead to the conclusion that the direct ethanol based dip coating can be an alternative economically viable process for the fabrication of earth abundant CNTS absorber layers for thin film solar cells.

  5. Oxidation of phosphine by sulfur or selenium involving a catalytic ...

    Indian Academy of Sciences (India)

    Administrator

    P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

  6. Experimental demonstration of 608Gbit/s short reach transmission employing half-cycle 16QAM Nyquist-SCM signal and direct detection with 25Gbps EML.

    Science.gov (United States)

    Zhong, Kangping; Zhou, Xian; Wang, Yiguang; Wang, Liang; Yuan, Jinhui; Yu, Changyuan; Lau, Alan Pak Tao; Lu, Chao

    2016-10-31

    In this paper, we experimentally demonstrated an IM/DD short reach transmission system with a total capacity of 608Gbit/s (net capacity of 565.4Gbit/s exclude 7% FEC overhead) employing half-cycle 16QAM Nyquist-SCM signal and 25Gbps EML at O band. Direct detection-faster than Nyquist (DD-FTN) technique was employed to compensate channel impairments. Number of taps of DD-LMS and tap coefficient of post filter in DD-FTN were experimentally studied for different baud rates. Single-lane 152Gbit/s transmission over 10km of SSMF was experimentally demonstrated. Employing a 4-lanes LAN-WDM architecture, a total capacity of 608Gbit/s transmission over 2km was successfully achieved with a receiver sensitivity lower than -4dBm. To the best of authors' knowledge, this is the highest reported baud rate of half-cycle 16QAM Nyquist-SCM signal and the highest bit rate employing IM/DD and 25Gbps EML in a four lanes LAN-WDM architecture for short reach systems in the O band.

  7. Conjugated oestrogen during the menstrual cycle measured by a direct radioimmunoassay with an antiserum prepared against oestradiol-17-glucosiduronate-(C-6)-BSA conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Honjo, H.; Otsubo, K.; Yasuda, J.; Kitawaki, J.; Okada, H. (Department of Obstetrics and Gynaecology, Kyoto Prefectural University of Medicine, Kyoto); Ohkubo, T.; Nambara, T. (Pharmaceutical Institute, Tohoku University, Sendai, Japan)

    1984-01-01

    Early morning and 24 h urine samples and serum were collected daily throughout the menstrual cycle in women. Urinary oestradiol-17-glucosiduronate (E/sub 2/-17G) was measured with a direct radioimmunoassay whose antiserum has been prepared against E/sub 2/-17-G-(C-6)-bovine serum albumin conjugate and was very specific. On the average, E/sub 2/-17-G in early morning and 24 h urine samples showed a prominent peak one day before the peak of urinary LH. The time relationship between these urinary E/sub 2/-17-G and serum E/sub 2/ levels and peaks was also investigated.

  8. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  9. Vapor-Driven Propulsion of Catalytic Micromotors

    Science.gov (United States)

    Dong, Renfeng; Li, Jinxing; Rozen, Isaac; Ezhilan, Barath; Xu, Tailin; Christianson, Caleb; Gao, Wei; Saintillan, David; Ren, Biye; Wang, Joseph

    2015-08-01

    Chemically-powered micromotors offer exciting opportunities in diverse fields, including therapeutic delivery, environmental remediation, and nanoscale manufacturing. However, these nanovehicles require direct addition of high concentration of chemical fuel to the motor solution for their propulsion. We report the efficient vapor-powered propulsion of catalytic micromotors without direct addition of fuel to the micromotor solution. Diffusion of hydrazine vapor from the surrounding atmosphere into the sample solution is instead used to trigger rapid movement of iridium-gold Janus microsphere motors. Such operation creates a new type of remotely-triggered and powered catalytic micro/nanomotors that are responsive to their surrounding environment. This new propulsion mechanism is accompanied by unique phenomena, such as the distinct off-on response to the presence of fuel in the surrounding atmosphere, and spatio-temporal dependence of the motor speed borne out of the concentration gradient evolution within the motor solution. The relationship between the motor speed and the variables affecting the fuel concentration distribution is examined using a theoretical model for hydrazine transport, which is in turn used to explain the observed phenomena. The vapor-powered catalytic micro/nanomotors offer new opportunities in gas sensing, threat detection, and environmental monitoring, and open the door for a new class of environmentally-triggered micromotors.

  10. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is ...

  11. Catalytic detritiation of water

    International Nuclear Information System (INIS)

    Rogers, M.L.; Lamberger, P.H.; Ellis, R.E.; Mills, T.K.

    1977-01-01

    A pilot-scale system has been used at Mound Laboratory to investigate the catalytic detritiation of water. A hydrophobic, precious metal catalyst is used to promote the exchange of tritium between liquid water and gaseous hydrogen at 60 0 C. Two columns are used, each 7.5 m long by 2.5 cm ID and packed with catalyst. Water flow is 5-10 cm 3 /min and countercurrent hydrogen flow is 9,000-12,000 cm 3 /min. The equipment, except for the columns, is housed in an inert atmosphere glovebox and is computer controlled. The hydrogen is obtained by electrolysis of a portion of the water stream. Enriched gaseous tritium is withdrawn for further enrichment. A description of the system is included along with an outline of its operation. Recent experimental data are discussed

  12. Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

    Science.gov (United States)

    Habershon, Scott

    2016-04-12

    In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

  13. Hydrophilic Pt nanoflowers: synthesis, crystallographic analysis and catalytic performance.

    Science.gov (United States)

    Mourdikoudis, Stefanos; Altantzis, Thomas; Liz-Marzán, Luis M; Bals, Sara; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge

    2016-05-21

    Water-soluble Pt nanoflowers (NFs) were prepared by diethylene glycol-mediated reduction of Pt acetylacetonate (Pt(acac) 2 ) in the presence of polyethylenimine. Advanced electron microscopy analysis showed that the NFs consist of multiple branches with a truncated cubic morphology and different crystallographic orientations. We demonstrate that the nature of the solvent strongly influences the resulting morphology. The catalytic performance of the Pt NFs in 4-nitrophenol reduction was found to be superior to that of other nanoparticle-based catalysts. Additionally, the Pt NFs display good catalytic reusability with no loss of activity after five consecutive cycles.

  14. Processing and structural characterization of porous reforming catalytic films

    International Nuclear Information System (INIS)

    Hou Xianghui; Williams, Jey; Choy, Kwang-Leong

    2006-01-01

    Nickel-based catalysts are often used to reform methanol into hydrogen. The preparation and installation of these catalysts are costly and laborious. As an alternative, directly applying catalytic films onto the separator components can improve the manufacturing efficiency. This paper reports the successful deposition of adherent porous NiO-Al 2 O 3 -based catalytic films with well-controlled stoichiometry, using a single-step Aerosol Assisted Chemical Vapour Deposition (AACVD) method. The microstructure, composition and crystalline phase of the as-deposited catalytic films are characterized using a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared (FTIR) Spectrometer. The results have demonstrated the capability of AACVD to produce porous NiO-Al 2 O 3 -based catalytic films

  15. Report on coal refining and chemical equipment analogous to coal liquefaction equipment in fiscal 1981. Maintenance of equipment for direct desulfurization, indirect desulfurization, and fluidized catalytic cracking; 1981 nendo sekitan ekika ruiji seiyu seisei oyobi kagaku sochi ni kansuru chosa hokokusho. Chokudatsu, kandatsu, ryudo sesshoku bunkai sochi no hozen

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-07-01

    This questionnaire survey was intended to investigate the actual state of maintenance such as materials used, conditions for use, anti-corrosion measures, and cases and handling of damage, concerning primary apparatus in the direct/indirect desulfurization equipment and the fluidized catalytic crackers, which are owned by each oil refinery and which are analogous to coal liquefaction equipment. The questionnaire was intended for the following equipment and apparatus, with the actual state of their maintenance investigated. 1. Questionnaire concerning maintenance of direct desulfurization (reactor, high temperature separation tank, material furnace tube, reactor exit piping, high temperature heat exchanger, low temperature heat exchanger, and pressure reducing valve), 2. Questionnaire concerning maintenance of indirect desulfurization (reactor, high temperature separation tank, material furnace tube, reactor exit piping, high temperature heat exchanger, low temperature heat exchanger, and pressure reducing valve), 3. Questionnaire concerning maintenance of fluidized catalytic cracker (reactor, regeneration tower, riser pipe, and fractionator bottom pump). The questionnaire this time was distributed to 27 domestic oil companies, with the reply received from 23 of them. The replies were summarized by each type of equipment. Shown at the back of the report were the cases of damage and handling in FCC's and reactors. (NEDO)

  16. Controlled synthesis of graphitic carbon-encapsulated α-Fe2O3 nanocomposite via low-temperature catalytic graphitization of biomass and its lithium storage property

    International Nuclear Information System (INIS)

    Wu, Feng; Huang, Rong; Mu, Daobin; Wu, Borong; Chen, Yongjian

    2016-01-01

    Highlights: • Facile synthesis of graphitic carbon/α-Fe 2 O 3 nano-sized anode composite. • In situ low temperature catalytic graphitization of biomass material. • Onion-like graphitic carbon layers conformally encapsulating around α-Fe 2 O 3 core. • High lithium storage properties, especially, outstanding cycle performance. - Abstract: A delicate structure of graphitic carbon-encapsulated α-Fe 2 O 3 nanocomposite is in situ constructed via “Absorption–Catalytic graphitization–Oxidation” strategy, taking use of biomass matter of degreasing cotton as carbon precursor and solution reservoir. With the assistance of the catalytic graphitization effect of iron core, onion-like graphitic carbon (GC) shell is made directly from the biomass at low temperature (650 °C). The nanosized α-Fe 2 O 3 particles would effectively mitigate volumetric strain and shorten Li + transport path during charge/discharge process. The graphitic carbon shells may promote charge transfer and protect active particles from directly exposing to electrolyte to maintain interfacial stability. As a result, the as-prepared α-Fe 2 O 3 @GC composite displays an outstanding cycle performance with a reversible capacity of 1070 mA h g −1 after 430 cycles at 0.2C, as well as a good rate capability of ∼ 950 mA h g −1 after 100 cycles at 1C and ∼ 850 mA h g −1 even up to 200 cycles at a 2C rate.

  17. Catalytic CO Oxidation over Au Nanoparticles Loaded Nanoporous Nickel Phosphate Composite

    Directory of Open Access Journals (Sweden)

    Xiaonan Leng

    2015-01-01

    Full Text Available Au/nickel phosphate-5 (Au/VSB-5 composite with the noble metal loading amount of 1.43 wt.% is prepared by using microporous VSB-5 nanocrystals as the support. Carbon monoxide (CO oxidation reaction is carried out over the sample with several catalytic cycles. Complete conversion of CO is achieved at 238°C over the catalyst at the first catalytic cycle. The catalytic activity improved greatly at the second cycle with the complete conversion fulfilled at 198°C and preserved for the other cycles. A series of experiments such as X-ray diffraction (XRD, high resolution transmission electron microscopy (HRTEM, ultraviolet-visible (UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS are carried out to characterize the catalysts before and after the reaction to study the factors influencing this promotion at the second cycle.

  18. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  19. Direct observation of the phase space footprint of a painting injection in the Rapid Cycling Synchrotron at the Japan Proton Accelerator Research Complex

    Directory of Open Access Journals (Sweden)

    P. K. Saha

    2009-04-01

    Full Text Available The 3 GeV Rapid Cycling Synchrotron (RCS at Japan Proton Accelerator Research Complex is nearly at the operational stage with regard to the beam commissioning aspects. Recently, the design painting injection study has been commenced with the aim of high output beam power at the extraction. In order to observe the phase space footprint of the painting injection, a method was developed utilizing a beam position monitor (BPM in the so-called single pass mode. The turn-by-turn phase space coordinates of the circulating beam directly measured using a pair of BPMs entirely positioned in drift space, and the calculated transfer matrices from the injection point to the pair of BPMs with several successive turns were used together in order to obtain the phase space footprint of the painting injection. There are two such pairs of BPMs placed in two different locations in the RCS, the results from which both agreed and were quite consistent with what was expected.

  20. Direct observation of the phase space footprint of a painting injection in the Rapid Cycling Synchrotron at the Japan Proton Accelerator Research Complex

    Science.gov (United States)

    Saha, P. K.; Shobuda, Y.; Hotchi, H.; Hayashi, N.; Takayanagi, T.; Harada, H.; Irie, Y.

    2009-04-01

    The 3 GeV Rapid Cycling Synchrotron (RCS) at Japan Proton Accelerator Research Complex is nearly at the operational stage with regard to the beam commissioning aspects. Recently, the design painting injection study has been commenced with the aim of high output beam power at the extraction. In order to observe the phase space footprint of the painting injection, a method was developed utilizing a beam position monitor (BPM) in the so-called single pass mode. The turn-by-turn phase space coordinates of the circulating beam directly measured using a pair of BPMs entirely positioned in drift space, and the calculated transfer matrices from the injection point to the pair of BPMs with several successive turns were used together in order to obtain the phase space footprint of the painting injection. There are two such pairs of BPMs placed in two different locations in the RCS, the results from which both agreed and were quite consistent with what was expected.

  1. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)

    2013-11-01

    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  2. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. ... enhancement was realized by catalyst design, appropriate choice of reactor, better injection and .... Gas–liquid and liquid–solid transport processes in catalytic reactors.5.

  3. Ni-Catalyzed Dehydrogenative Cross-Coupling: Direct Transformation of Aldehydes to Esters and Amides

    Science.gov (United States)

    Whittaker, Aaron M.; Dong, Vy M.

    2015-01-01

    By exploring a new mode of Ni-catalyzed cross-coupling, we have developed a protocol to transform both aromatic and aliphatic aldehydes into either esters or amides directly. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. We present mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C–H bond. PMID:25424967

  4. Cycling the Hot CNO: A Teaching Methodology

    Science.gov (United States)

    Frost-Schenk, J. W.; Diget, C. Aa.; Bentley, M. A.; Tuff, A.

    2018-01-01

    An interactive activity to teach the hot Carbon, Nitrogen and Oxygen (HCNO) cycle is proposed. Justification for why the HCNO cycle is important is included via an example of x-ray bursts. The activity allows teaching and demonstration of half-life, nuclear isotopes, nuclear reactions, protons and a-particles, and catalytic processes. Whilst the…

  5. Control-rod, pressure and flow-induced accident and transient analysis of a direct-cycle, supercritical-pressure, light-water-cooled fast breeder reactor

    International Nuclear Information System (INIS)

    Kitoh, Kazuaki; Koshizuka, Seiichi; Oka, Yoshiaki

    1996-01-01

    The features of the direct-cycle, supercritical-pressure, light-water-cooled fast breeder reactor (SCFBR) are high thermal efficiency and simple reactor system. The safety principle is basically the same as that of an LWR since it is a water-cooled reactor. Maintaining the core flow is the basic safety requirement of the reactor, since its coolant system is the one through type. The transient behaviors at control rod, pressure and flow-induced abnormalities are analyzed and presented in this paper. The results of flow-induced transients of SCFBR were reported at ICONE-3, though pressure change was neglected. The change of fuel temperature distribution is also considered for the analysis of the rapid reactivity-induced transients such as control rod withdrawal. Total loss of flow and pump seizure are analyzed as the accidents. Loss of load, control rod withdrawal from the normal operation, loss of feedwater heating, inadvertent start of an auxiliary feedwater pump, partial loss of coolant flow and loss of external power are analyzed as the transients. The behavior of the flow-induced transients is not so much different from the analyses assuming constant pressure. Fly wheels should be equipped with the feedwater pumps to prolong the coast-down time more than 10s and to cope with the total loss of flow accident. The coolant density coefficient of the SCFBR is less than one tenth of a BWR in which the recirculation flow is used for the power control. The over pressurization transients at the loss of load is not so severe as that of a BWR. The power reaches 120%. The minimum deterioration heat flux ratio (MDHFR) and the maximum pressure are sufficiently lower than the criteria; MDHFR above 1.0 and pressure ratio below 1.10 of 27.5 MPa, maximum pressure for operation. Among the reactivity abnormalities, the control rod withdrawal transient from the normal operation is analyzed

  6. The daytime cycle in dust aerosol direct radiative effects observed in the central Sahara during the Fennec campaign in June 2011

    KAUST Repository

    Banks, Jamie R.

    2014-12-16

    © 2014. American Geophysical Union. All Rights Reserved. The direct clear-sky radiative effect (DRE) of atmospheric mineral dust is diagnosed over the Bordj Badji Mokhtar (BBM) supersite in the central Sahara during the Fennec campaign in June 2011. During this period, thick dust events were observed, with aerosol optical depth values peaking at 3.5. Satellite observations from Meteosat-9 are combined with ground-based radiative flux measurements to obtain estimates of DRE at the surface, top-of-atmosphere (TOA), and within the atmosphere. At TOA, there is a distinct daytime cycle in net DRE. Both shortwave (SW) and longwave (LW) DRE peak around noon and induce a warming of the Earth-atmosphere system. Toward dusk and dawn, the LW DRE reduces while the SW effect can switch sign triggering net radiative cooling. The net TOA DRE mean values range from -9 Wm-2 in the morning to heating of +59 Wm-2 near midday. At the surface, the SW dust impact is larger than at TOA: SW scattering and absorption by dust results in a mean surface radiative cooling of 145Wm-2. The corresponding mean surface heating caused by increased downward LW emission from the dust layer is a factor of 6 smaller. The dust impact on the magnitude and variability of the atmospheric radiative divergence is dominated by the SW cooling of the surface, modified by the smaller SW and LW effects at TOA. Consequently, dust has a mean daytime net radiative warming effect on the atmosphere of 153Wm-2.

  7. The Miller cycle effects on improvement of fuel economy in a highly boosted, high compression ratio, direct-injection gasoline engine: EIVC vs. LIVC

    International Nuclear Information System (INIS)

    Li, Tie; Gao, Yi; Wang, Jiasheng; Chen, Ziqian

    2014-01-01

    Highlights: • At high load, LIVC is superior over EIVC in improving fuel economy. • The improvement with LIVC is due to advanced combustion phasing and increased pumping work. • At low load, EIVC is better than LIVC in improving fuel economy. • Pumping loss with EIVC is smaller than with LIVC at low load. • But heat release rate with EIVC is slower than with LIVC. - Abstract: A combination of downsizing, highly boosting and direct injection (DI) is an effective way to improve fuel economy of gasoline engines without the penalties of reduced torque or power output. At high loads, however, knock problem becomes severer when increasing the intake boosting. As a compromise, geometric compression ratio (CR) is usually reduced to mitigate knock, and the improvement of fuel economy is discounted. Application of Miller cycle, which can be realized by either early or late intake valve closing (EIVC or LIVC), has the potential to reduce the effective CR and suppress knock. In this paper, the effects of EIVC and LIVC on the fuel economy of a boosted DI gasoline production engine reformed with a geometric CR of 12.0 are experimentally compared at low and high loads. Compared to the original production engine with CR 9.3, at the high load operation, the brake specific fuel consumption (BSFC) is improved by 4.7% with CR12.0 and LIVC, while the effect of EIVC on improving BSFC is negligibly small. At the low load operation, combined with CR12.0, LIVC and EIVC improve the fuel economy by 6.8% and 7.4%, respectively, compared to the production engine. The mechanism behind the effects of LIVC and EIVC on improving the fuel economy is discussed. These results will be a valuable reference for engine designers and researchers

  8. Catalytic hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Wayland, B.B.

    1992-12-01

    This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions.

  9. Promotion and Suppression of Centriole Duplication Are Catalytically Coupled through PLK4 to Ensure Centriole Homeostasis

    Directory of Open Access Journals (Sweden)

    Minhee Kim

    2016-08-01

    Full Text Available PLK4 is the major kinase driving centriole duplication. Duplication occurs only once per cell cycle, forming one new (or daughter centriole that is tightly engaged to the preexisting (or mother centriole. Centriole engagement is known to block the reduplication of mother centrioles, but the molecular identity responsible for the block remains unclear. Here, we show that the centriolar cartwheel, the geometric scaffold for centriole assembly, forms the identity of daughter centrioles essential for the block, ceasing further duplication of the mother centriole to which it is engaged. To ensure a steady block, we found that the cartwheel requires constant maintenance by PLK4 through phosphorylation of the same substrate that drives centriole assembly, revealing a parsimonious control in which “assembly” and “block for new assembly” are linked through the same catalytic reaction to achieve homeostasis. Our results support a recently deduced model that the cartwheel-bound PLK4 directly suppresses centriole reduplication.

  10. Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: Crucial role of proton-transfer shuttles in the PNP-Ir system

    KAUST Repository

    Qu, Shuanglin

    2014-04-02

    Kempe et al. and Milstein et al. have recently advanced the dehydrogenative coupling methodology to synthesize pyrroles from secondary alcohols (e.g., 3) and β-amino alcohols (e.g., 4), using PNP-Ir (1) and PNN-Ru (2) pincer complexes, respectively. We herein present a DFT study to characterize the catalytic mechanism of these reactions. After precatalyst activation to give active 1A/2A, the transformation proceeds via four stages: 1A/2A-catalyzed alcohol (3) dehydrogenation to give ketone (11), base-facilitated C-N coupling of 11 and 4 to form an imine-alcohol intermediate (18), base-promoted cyclization of 18, and catalyst regeneration via H2 release from 1R/2R. For alcohol dehydrogenations, the bifunctional double hydrogen-transfer pathway is more favorable than that via β-hydride elimination. Generally, proton-transfer (H-transfer) shuttles facilitate various H-transfer processes in both systems. Notwithstanding, H-transfer shuttles play a much more crucial role in the PNP-Ir system than in the PNN-Ru system. Without H-transfer shuttles, the key barriers up to 45.9 kcal/mol in PNP-Ir system are too high to be accessible, while the corresponding barriers (<32.0 kcal/mol) in PNN-Ru system are not unreachable. Another significant difference between the two systems is that the addition of alcohol to 1A giving an alkoxo complex is endergonic by 8.1 kcal/mol, whereas the addition to 2A is exergonic by 8.9 kcal/mol. The thermodynamic difference could be the main reason for PNP-Ir system requiring lower catalyst loading than the PNN-Ru system. We discuss how the differences are resulted in terms of electronic and geometric structures of the catalysts and how to use the features in catalyst development. © 2014 American Chemical Society.

  11. Catalytic oxidation of soot over alkaline niobates

    International Nuclear Information System (INIS)

    Pecchi, G.; Cabrera, B.; Buljan, A.; Delgado, E.J.; Gordon, A.L.; Jimenez, R.

    2013-01-01

    Highlights: ► No previous reported studies about alkaline niobates as catalysts for soot oxidation. ► NaNbO 3 and KNbO 3 perovskite-type oxides show lower activation energy than other lanthanoid perovskite-type oxides. ► The alkaline niobate does not show deactivation by metal loss. - Abstract: The lack of studies in the current literature about the assessment of alkaline niobates as catalysts for soot oxidation has motivated this research. In this study, the synthesis, characterization and assessment of alkaline metal niobates as catalysts for soot combustion are reported. The solids MNbO 3 (M = Li, Na, K, Rb) are synthesized by a citrate method, calcined at 450 °C, 550 °C, 650 °C, 750 °C, and characterized by AAS, N 2 adsorption, XRD, O 2 -TPD, FTIR and SEM. All the alkaline niobates show catalytic activity for soot combustion, and the activity depends basically on the nature of the alkaline metal and the calcination temperature. The highest catalytic activity, expressed as the temperature at which combustion of carbon black occurs at the maximum rate, is shown by KNbO 3 calcined at 650 °C. At this calcination temperature, the catalytic activity follows an order dependent on the atomic number, namely: KNbO 3 > NaNbO 3 > LiNbO 3 . The RbNbO 3 solid do not follow this trend presumably due to the perovskite structure was not reached. The highest catalytic activity shown by of KNbO 3 , despite the lower apparent activation energy of NaNbO 3 , stress the importance of the metal nature and suggests the hypothesis that K + ions are the active sites for soot combustion. It must be pointed out that alkaline niobate subjected to consecutive soot combustion cycles does not show deactivation by metal loss, due to the stabilization of the alkaline metal inside the perovskite structure.

  12. Catalytic bioreactors and methods of using same

    Science.gov (United States)

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  13. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne

    2007-01-01

    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  14. Synthesis and utilization of catalytically cracked cashew nut shell liquid in a diesel engine

    KAUST Repository

    Vedharaj, S.

    2015-09-30

    In this study, CNSL (Cashew nut shell liquid), an economically viable feedstock among the other contemporary resources, has been considered as an appropriate source of alternate fuel. Herein, CNSL was extracted from cashew nut outer shell, a waste product, through a unique approach of steam treatment process followed by mechanical crushing technique. In contrast to the past studies that have attempted to use unprocessed CNSL directly as substitute for diesel, this study has resorted to use processed CNSL by cracking it using zeolite catalyst. Thus, both the extraction of CNSL from cashew nut outer shell and processing of it through catalytic cracking process to help synthesize CC-CNSL (catalytically cracked CNSL) are different, which underscores the significance of the current work. In wake of adopting such distinct methodologies with fuel characterization, the properties of CC-CNSL such as viscosity and calorific value were figured out to be improved. Subsequently, CC-CNSL20 (20% CC-CNSL and 80% diesel) was tested at different fuel injection pressure such as 200 bar, 235 bar, 270 bar and 300 bar so as to optimize its use in a single cylinder diesel engine. From the engine experimental study, CC-CNSL20 was found to evince better engine performance than diesel and the composite emissions of CO (carbon monoxide), HC (hydrocarbon), NOX (oxides of nitrogen) and smoke, computed based on ISO 8178 D2 standard test cycle, were found to be better than diesel and incompliance with the legislative norms for genset.

  15. Synthesis and utilization of catalytically cracked cashew nut shell liquid in a diesel engine

    KAUST Repository

    Vedharaj, S.; Vallinayagam, R.; Yang, W.M.; Saravanan, C.G.; Roberts, William L.

    2015-01-01

    In this study, CNSL (Cashew nut shell liquid), an economically viable feedstock among the other contemporary resources, has been considered as an appropriate source of alternate fuel. Herein, CNSL was extracted from cashew nut outer shell, a waste product, through a unique approach of steam treatment process followed by mechanical crushing technique. In contrast to the past studies that have attempted to use unprocessed CNSL directly as substitute for diesel, this study has resorted to use processed CNSL by cracking it using zeolite catalyst. Thus, both the extraction of CNSL from cashew nut outer shell and processing of it through catalytic cracking process to help synthesize CC-CNSL (catalytically cracked CNSL) are different, which underscores the significance of the current work. In wake of adopting such distinct methodologies with fuel characterization, the properties of CC-CNSL such as viscosity and calorific value were figured out to be improved. Subsequently, CC-CNSL20 (20% CC-CNSL and 80% diesel) was tested at different fuel injection pressure such as 200 bar, 235 bar, 270 bar and 300 bar so as to optimize its use in a single cylinder diesel engine. From the engine experimental study, CC-CNSL20 was found to evince better engine performance than diesel and the composite emissions of CO (carbon monoxide), HC (hydrocarbon), NOX (oxides of nitrogen) and smoke, computed based on ISO 8178 D2 standard test cycle, were found to be better than diesel and incompliance with the legislative norms for genset.

  16. Chemically-modified cellulose paper as a microstructured catalytic reactor.

    Science.gov (United States)

    Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

    2015-01-15

    We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

  17. Hydrogen production via catalytic processing of renewable feedstocks

    International Nuclear Information System (INIS)

    Nazim Muradov; Franklyn Smith; Ali T-Raissi

    2006-01-01

    Landfill gas (LFG) and biogas can potentially become important feedstocks for renewable hydrogen production. The objectives of this work were: (1) to develop a catalytic process for direct reforming of CH 4 -CO 2 gaseous mixture mimicking LFG, (2) perform thermodynamic analysis of the reforming process using AspenPlus chemical process simulator, (3) determine operational conditions for auto-thermal (or thermo-neutral) reforming of a model CH 4 -CO 2 feedstock, and (4) fabricate and test a bench-scale hydrogen production unit. Experimental data obtained from catalytic reformation of the CH 4 -CO 2 and CH 4 -CO 2 -O 2 gaseous mixtures using Ni-catalyst were in a good agreement with the simulation results. It was demonstrated that catalytic reforming of LFG-mimicking gas produced hydrogen with the purity of 99.9 vol.%. (authors)

  18. Chemically-Modified Cellulose Paper as a Microstructured Catalytic Reactor

    Directory of Open Access Journals (Sweden)

    Hirotaka Koga

    2015-01-01

    Full Text Available We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

  19. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

    The catalytic activity and selectivity of niobium compounds including oxides, salts, organometallic compounds and others are outlined. The application of these compounds as catalysts to diversified reactions is reported. The nature and action of niobium catalysts are characteristic and sometimes anomalous, suggesting the necessity of basic research and the potential use as catalysts for important processes in the chemical industry. (Author) [pt

  20. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric

    2017-01-01

    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... and quantum state merging, and leads to a resource theory of decoupling....

  1. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    were characterized by infrared, electronic, electron paramagnetic resonance ... The catalytic oxidation property of ruthenium(III) complexes were also ... cies at room temperature. ..... aldehyde part of Schiff base ligands, catalytic activ- ity of new ...

  2. Development and test of a new catalytic converter for natural gas ...

    Indian Academy of Sciences (India)

    catalytic converter and a new natural gas engine such as compressed natural gas. (CNG) direct ..... bility to store oxygen from random gas flow within the substrate in comparison to flow through ..... and behaviour in the water–gas shift reaction.

  3. On acyclicity of games with cycles

    DEFF Research Database (Denmark)

    Andersson, Klas Olof Daniel; Hansen, Thomas Dueholm; Gurvich, Vladimir

    2010-01-01

    We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (di-graphs) that may contain directed cycles (di-cycles). We assume that all these di-cycles form one outcome c, for example, a draw. We obtain criteria...

  4. Using Life Cycle Revenue Loss and Monte Carlo simulation as a prior and direct assessment of consequences of un-wished events

    International Nuclear Information System (INIS)

    Muchiu, Chang; Lewins, J.D.

    1998-01-01

    In this paper we address the importance of including the consideration of revenue loss into the safety analysis as well as system optimisation and modify the traditional Life Cycle Cost (LCC) into Life Cycle Revenue Loss (LCRL) as the criterion of optimisation and a quantitative assessment of the consequence of un-wished ebents, such as system unavailability. Through the Monte Carlo simulation technique and a simple scenario of decision making in a bidding process, we demonstrate the feasibility of our new LCRL model

  5. Cycling the hot CNO: a teaching methodology

    Science.gov (United States)

    Frost-Schenk, J. W.; Diget, C. Aa; Bentley, M. A.; Tuff, A.

    2018-03-01

    An interactive activity to teach the hot Carbon, Nitrogen and Oxygen (HCNO) cycle is proposed. Justification for why the HCNO cycle is important is included via an example of x-ray bursts. The activity allows teaching and demonstration of half-life, nuclear isotopes, nuclear reactions, protons and α-particles, and catalytic processes. Whilst the process example is specific to astrophysics it may be used to teach more broadly about catalytic processes. This practical is designed for use with 10-20 participants, with the intention that the exercise will convey nuclear physics principles in a fun and interactive manner.

  6. CHANGES OF BUOYANT DENSITY DURING THE S-PHASE OF THE CELL-CYCLE - DIRECT EVIDENCE DEMONSTRATED IN ACUTE MYELOID-LEUKEMIA BY FLOW-CYTOMETRIC

    NARCIS (Netherlands)

    DAENEN, S; HUIGES, W; MODDERMAN, E; HALIE, MR

    Studies with synchronized or exponentially growing bacteria and mammalian cell lines are not able to demonstrate small changes in buoyant density during the cell cycle. Flowcytometric analysis of density separated acute myeloid leukemia cells, a system not dependent on time-related variables, shows

  7. NOx Direct Decomposition: Potentially Enhanced Thermodynamics and Kinetics on Chemically Modified Ferroelectric Surfaces

    Science.gov (United States)

    Kakekhani, Arvin; Ismail-Beigi, Sohrab

    2014-03-01

    NOx are regulated pollutants produced during automotive combustion. As part of an effort to design catalysts for NOx decomposition that operate in oxygen rich environment and permit greater fuel efficiency, we study chemistry of NOx on (001) ferroelectric surfaces. Changing the polarization at such surfaces modifies electronic properties and leads to switchable surface chemistry. Using first principles theory, our previous work has shown that addition of catalytic RuO2 monolayer on ferroelectric PbTiO3 surface makes direct decomposition of NO thermodynamically favorable for one polarization. Furthermore, the usual problem of blockage of catalytic sites by strong oxygen binding is overcome by flipping polarization that helps desorb the oxygen. We describe a thermodynamic cycle for direct NO decomposition followed by desorption of N2 and O2. We provide energy barriers and transition states for key steps of the cycle as well as describing their dependence on polarization direction. We end by pointing out how a switchable order parameter of substrate,in this case ferroelectric polarization, allows us to break away from some standard compromises for catalyst design(e.g. the Sabatier principle). This enlarges the set of potentially catalytic metals. Primary support from Toyota Motor Engineering and Manufacturing, North America, Inc.

  8. Catalytic hydrodeoxygenation of dibenzofuran

    Energy Technology Data Exchange (ETDEWEB)

    La Vopa, V.; Satterfield, C.N.

    The hydrodeoxygenation of dibenzofuran (DBF) on a sulfided NiMo/Al/sub 2/O/sub 3/ catalyst was studied at 350-390 C and 7.0 MPa. The major products isolated were single-ring hydrocarbons, cyclohexane predominating; the remainder were double-ring hydrocarbons, cyclohexylbenzene predominating. No oxygen-containing species other than water were isolated in any significant amount. The initial reactions in the hydrodeoxygenation of DBF are rate-limiting. The non-sulfided (oxide) catalyst is much less active, and double-ring products predominate over single-ring products. From studies of possible intermediates it appears that on a sulfided catalyst two pathways operate in parallel for the hydrodeoxygenation of dibenzofuran: (1) hydrogenation of DBF to hexahydro DBF, which reacts via 2-cyclohexylphenol to form signle-ring hydrocarbons; (2) direct hydrogenolysis via 2-phenylphenol, without prior ring hydrogenation, to form biphenyl and cyclohexylbenzene (a minor route). On this catalyst the overall reaction is first order with respect to hydrogen and to DBF and exhibits an apparent activation energy of 67 kJ/mol. 26 refs., 16 figs., 3 tabs.

  9. Catalytic Activity Control via Crossover between Two Different Microstructures

    KAUST Repository

    Zhou, Yuheng

    2017-09-08

    Metal nanocatalysts hold great promise for a wide range of heterogeneous catalytic reactions, while the optimization strategy of catalytic activity is largely restricted by particle size or shape control. Here, we demonstrate that a reversible microstructural control through the crossover between multiply-twinned nanoparticle (MTP) and single crystal (SC) can be readily achieved by solvent post-treatment on gold nanoparticles (AuNPs). Polar solvents (e.g. water, methanol) direct the transformation from MTP to SC accompanied by the disappearance of twinning and stacking faults. A reverse transformation from SC to MTP is achieved in non-polar solvent (e.g. toluene) mixed with thiol ligands. The transformation between two different microstructures is directly observed by in-situ TEM and leads to a drastic modulation of catalytic activity towards the gas-phase selective oxidation of alcohols. There is a quasi-linear relationship between TOFs and MTP concentrations. Based on the combined experimental and theoretical investigations of alcohol chemisorption on these nanocatalysts, we propose that the exposure of {211}-like microfacets associated with twin boundaries and stack faults accounts for the strong chemisorption of alcohol molecules on MTP AuNPs and thus the exceptionally high catalytic activity.

  10. Catalytic process for tritium exchange reaction

    International Nuclear Information System (INIS)

    Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

    2001-01-01

    The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

  11. Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

    Science.gov (United States)

    Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

    2005-05-03

    Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

  12. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  13. Fuel Flexible, Low Emission Catalytic Combustor for Opportunity Fuel Applications

    Energy Technology Data Exchange (ETDEWEB)

    Eteman, Shahrokh

    2013-06-30

    Limited fuel resources, increasing energy demand and stringent emission regulations are drivers to evaluate process off-gases or process waste streams as fuels for power generation. Often these process waste streams have low energy content and/or highly reactive components. Operability of low energy content fuels in gas turbines leads to issues such as unstable and incomplete combustion. On the other hand, fuels containing higher-order hydrocarbons lead to flashback and auto-ignition issues. Due to above reasons, these fuels cannot be used directly without modifications or efficiency penalties in gas turbine engines. To enable the use of these wide variety of fuels in gas turbine engines a rich catalytic lean burn (RCL®) combustion system was developed and tested in a subscale high pressure (10 atm.) rig. The RCL® injector provided stability and extended turndown to low Btu fuels due to catalytic pre-reaction. Previous work has shown promise with fuels such as blast furnace gas (BFG) with LHV of 85 Btu/ft3 successfully combusted. This program extends on this work by further modifying the combustor to achieve greater catalytic stability enhancement. Fuels containing low energy content such as weak natural gas with a Lower Heating Value (LHV) of 6.5 MJ/m3 (180 Btu/ft3 to natural gas fuels containing higher hydrocarbon (e.g ethane) with LHV of 37.6 MJ/m3 (1010 Btu/ft3) were demonstrated with improved combustion stability; an extended turndown (defined as the difference between catalytic and non-catalytic lean blow out) of greater than 250oF was achieved with CO and NOx emissions lower than 5 ppm corrected to 15% O2. In addition, for highly reactive fuels the catalytic region preferentially pre-reacted the higher order hydrocarbons with no events of flashback or auto-ignition allowing a stable and safe operation with low NOx and CO emissions.

  14. Carbon nanofibers: a versatile catalytic support

    Directory of Open Access Journals (Sweden)

    Nelize Maria de Almeida Coelho

    2008-09-01

    Full Text Available The aim of this article is present an overview of the promising results obtained while using carbon nanofibers based composites as catalyst support for different practical applications: hydrazine decomposition, styrene synthesis, direct oxidation of H2S into elementary sulfur and as fuel-cell electrodes. We have also discussed some prospects of the use of these new materials in total combustion of methane and in ammonia decomposition. The macroscopic carbon nanofibers based composites were prepared by the CVD method (Carbon Vapor Deposition employing a gaseous mixture of hydrogen and ethane. The results showed a high catalytic activity and selectivity in comparison to the traditional catalysts employed in these reactions. The fact was attributed, mainly, to the morphology and the high external surface of the catalyst support.

  15. Catalytic processes for cleaner fuels

    International Nuclear Information System (INIS)

    Catani, R.; Marchionna, M.; Rossini, S.

    1999-01-01

    More stringent limitations on vehicle emissions require different measurement: fuel reformulation is one of the most important and is calling for a noticeable impact on refinery assets. Composition rangers of the future fuels have been defined on a time scale. In this scenario the evolution of catalytic technologies becomes a fundamental tool for allowing refinery to reach the fixed-by-law targets. In this paper, the refinery process options to meet each specific requirements of reformulated fuels are surveyed [it

  16. Ultrasound assisted co-precipitation of nanostructured CuO-ZnO-Al2O3 over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME.

    Science.gov (United States)

    Allahyari, Somaiyeh; Haghighi, Mohammad; Ebadi, Amanollah; Hosseinzadeh, Shahin

    2014-03-01

    Nanostructured CuO-ZnO-Al2O3/HZSM-5 was synthesized from nitrate and acetate precursors using ultrasound assisted co-precipitation method under different irradiation powers. The CuO-ZnO-Al2O3/HZSM-5 nanocatalysts were characterized using XRD, FESEM, BET, FTIR and EDX Dot-mapping analyses. The results indicated precursor type and irradiation power have significant influences on phase structure, morphology, surface area and functional groups. It was observed that the acetate formulated CuO-ZnO-Al2O3/HZSM-5 nanocatalyst have smaller CuO crystals with better dispersion and stronger interaction between components in comparison to nitrate based nanocatalysts. Ultrasound assisted co-precipitation synthesis method resulted in nanocatalyst with more uniform morphology compared to conventional method and increasing irradiation power yields smaller particles with better dispersion and higher surface area. Additionally the crystallinity of CuO is lower at high irradiation powers leading to stronger interaction between metal oxides. The nanocatalysts performance were tested at 200-300 °C, 10-40 bar and space velocity of 18,000-36,000 cm(3)/g h with the inlet gas composition of H2/CO = 2/1 in a stainless steel autoclave reactor. The acetate based nanocatalysts irradiated with higher levels of power exhibited better reactivity in terms of CO conversion and DME yield. While there is an optimal temperature for CO conversion and DME yield in direct synthesis of DME, CO conversion and DME yield both increase with the pressure increase. Furthermore ultrasound assisted co-precipitation method yields more stable CuO-ZnO-Al2O3/HZSM-5 nanocatalyst while conventional precipitated nanocatalyst lost their activity ca. 18% and 58% in terms of CO conversion and DME yield respectively in 24 h time on stream test.

  17. Structured materials for catalytic and sensing applications

    Science.gov (United States)

    Hokenek, Selma

    The optical and chemical properties of the materials used in catalytic and sensing applications directly determine the characteristics of the resultant catalyst or sensor. It is well known that a catalyst needs to have high activity, selectivity, and stability to be viable in an industrial setting. The hydrogenation activity of palladium catalysts is known to be excellent, but the industrial applications are limited by the cost of obtaining catalyst in amounts large enough to make their use economical. As a result, alloying palladium with a cheaper, more widely available metal while maintaining the high catalytic activity seen in monometallic catalysts is, therefore, an attractive option. Similarly, the optical properties of nanoscale materials used for sensing must be attuned to their application. By adjusting the shape and composition of nanoparticles used in such applications, very fine changes can be made to the frequency of light that they absorb most efficiently. The design, synthesis, and characterization of (i) size controlled monometallic palladium nanoparticles for catalytic applications, (ii) nickel-palladium bimetallic nanoparticles and (iii) silver-palladium nanoparticles with applications in drug detection and biosensing through surface plasmon resonance, respectively, will be discussed. The composition, size, and shape of the nanoparticles formed were controlled through the use of wet chemistry techniques. After synthesis, the nanoparticles were analyzed using physical and chemical characterization techniques such as X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy- Energy-Dispersive Spectrometry (STEM-EDX). The Pd and Ni-Pd nanoparticles were then supported on silica for catalytic testing using mass spectrometry. The optical properties of the Ag-Pd nanoparticles in suspension were further investigated using ultraviolet-visible spectrometry (UV-Vis). Monometallic palladium particles have

  18. Ammonium generation during SRAT cycle

    International Nuclear Information System (INIS)

    Hsu, C.W.

    1992-01-01

    During the IDMS noble-metal demonstration runs ammonium nitrate deposition was found in the vessel vent system of the feed preparation area. In the bench-scale experiments of studying the hydrogen generation during the sludge treatment cycle, ammonium ion production was also monitored. It was found that: During a simulation of the DWPF Cold Chemical Runs SRAT cycle no detectable amount of ammonium ions was generated when treating a non-noble-metal containing sludge simulant according to the nitric acid flowsheet. Ammonium ions were generated during the SRAT-SME cycle when treating the noble-metal containing sludge with either formic acid or nitric acid/late-washing PHA. This is due to the reaction between formic acid and nitrate catalyzed by the noble metals in the sludge simulant. Ammonium ion production closely followed the hydrogen evolution from the catalytic decomposition of formic acid. This report summarizes the results of the production of ammonia during the SRAT cycle

  19. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries.

    Science.gov (United States)

    Roberts, Matthew R; Madsen, Alex; Nicklin, Chris; Rawle, Jonathan; Palmer, Michael G; Owen, John R; Hector, Andrew L

    2014-04-03

    The phase changes that occur during discharge of an electrode comprised of LiFePO 4 , carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO 4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate.

  20. Investigation of combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine system

    International Nuclear Information System (INIS)

    Yin Juan; Weng Yiwu

    2011-01-01

    The goals of this research were to investigate the combustion and thermodynamic performance of a lean burn catalytic combustion gas turbine. The characteristics of lean burn catalytic combustion were investigated by utilising 1D heterogeneous plug flow model which was validated by experiments. The effects of operating parameters on catalytic combustion were numerically analysed. The system models were built in ASPEN Plus and three independent design variables, i.e. compressor pressure ratio (PR), regenerator effectiveness (RE) and turbine inlet temperature (TIT) were selected to analyse the thermodynamic performance of the thermal cycle. The main results show that: simulations from 1D heterogeneous plug flow model can capture the trend of catalytic combustion and describe the behavior of the catalytic monolith in detail. Inlet temperature is the most significant parameter that impacts operation of the catalytic combustor. When TIT and RE are constant, the increase of PR results in lowering the inlet temperature of the catalytic combustor, which results in decreasing methane conversion. The peak thermal efficiency and the optimal PR at a constant TIT increase with the increase of TIT; and at the constant PR, the thermal efficiency increases with the increase of TIT. However, with lower TIT conditions, the optimal PR and the peak efficiency at a constant TIT of the LBCCGT cycle are relative low to that of the conventional cycle. When TIT and PR are constant, the decrease of RE may result in lower methane conversion. The influences of RE on the methane conversion and the thermal efficiency are more significant at higher PRs. The higher thermal efficiency for the lower RE is achieved at lower PR.

  1. Driving and engine cycles

    CERN Document Server

    Giakoumis, Evangelos G

    2017-01-01

    This book presents in detail the most important driving and engine cycles used for the certification and testing of new vehicles and engines around the world. It covers chassis and engine-dynamometer cycles for passenger cars, light-duty vans, heavy-duty engines, non-road engines and motorcycles, offering detailed historical information and critical review. The book also provides detailed examples from SI and diesel engines and vehicles operating during various cycles, with a focus on how the engine behaves during transients and how this is reflected in emitted pollutants, CO2 and after-treatment systems operation. It describes the measurement methods for the testing of new vehicles and essential information on the procedure for creating a driving cycle. Lastly, it presents detailed technical specifications on the most important chassis-dynamometer cycles around the world, together with a direct comparison of those cycles.

  2. Production of filamentous carbon and H{sub 2} by solarthermal catalytic cracking of CH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Kirillov, V; Kuvshinov, G [Boreskov Inst. of Catalysis (Russian Federation); Reller, A [Hamburg Univ., Hamburg (Germany); Steinfeld, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The catalytic thermal decomposition of methane has been experimentally studied using high-temperature solar process heat. Nickel catalyst particles, fluidized in methane, were directly irradiated at the PSI solar furnace. Carbon deposition consisted of randomly interlaced filaments that grew as fibers and hollow nanotubes (of approx. 30 nm diameter) originating at each catalytic particle. (author) 4 figs., 7 refs.

  3. Trends in catalytic NO decomposition over transition metal surfaces

    DEFF Research Database (Denmark)

    Falsig, Hanne; Bligaard, Thomas; Rass-Hansen, Jeppe

    2007-01-01

    The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional...... theory calculations. We show specifically why the key problem in using transition metal surfaces to catalyze direct NO decomposition is their significant relative overbinding of atomic oxygen compared to atomic nitrogen....

  4. Direct measuring of single-cycle mid-IR light bullets path length in LiF by the laser coloration method

    Directory of Open Access Journals (Sweden)

    Chekalin Sergey

    2017-01-01

    Full Text Available A colour-centre structure formed in a LiF crystal under filamentation of a femtosecond mid-IR laser pulse with a power slightly exceeding the critical power for self-focusing has been experimentally and theoretically investigated. A single-cycle light bullet was recorded for the first time by observation of strictly periodic oscillations for the density of the color centers induced in an isotropic LiF crystal under filamentation of a laser beam with a wavelength tuned in the range from 2600 to 3900 nm, which is due to the periodic change in the light field amplitude in the light bullet formed under filamentation under propagation in dispersive medium. The light bullet path length was not more than one millimeter.

  5. Radioimmunoassay of estriol-16-glucuronide using tritiated and radioiodinated radioligands: direct radioimmunoassay of urinary estriol-16-glucuronide during the menstrual cycle

    International Nuclear Information System (INIS)

    Stanczyk, F.Z.; Miyakawa, I.; Soares, J.R.; Goebelsmann, U.

    1979-01-01

    Estriol-16-glucuronide-[ 125 I]-iodohistamine (E 3 -16G-[ 125 ]) was prepared and utilized in a radioimmunoassay (RIA) in conjunction with anti-estriol-16-glucuronide-bovine serum albumin (E 3 -16G-BSA) serum (RIA No.1). This RIA was then compared with two other RIA methods employing [ 3 H]-labeled estriol-16-glucuronide (E 3 -16G) together with either anti-E 3 -16G-BAS serum (RIA No.2) or anti-estriol-16-glucuronide-2-azobenzoic acid-bovine serum albumin (E 3 -16G-2-BSA) serum (RIA No. 3). All three RIA's were accurate and precise, however, they differed in assay sensitivity and specificity. Most sensitive was RIA No.1 and least sensitive was RIA No.3. Both RIA's No.1 and 2 were less specific than RIA No.3. since unconjugated estriol and estrone 3-sulfate exhibited large and comparable cross-reactions in RIA's No.1 and 2, averaging 50% and 41% respectively. Furthermore, measurement of E 3 -16G in 10 different urine aliquots collected from non-pregnant women employing RIA's No. 1-3 showed that RIA's No. 1 and 2 yielded comparable results, however, the results obtained by RIA No.3 were, on the average, 26% lower than the mean of the values measured with RIA's No. 1 and 2. Consequently, RIA Bo.3 was used to measure daily 24-hour urinary E 3 -16G excretion in 7 women throughout an entire menstrual cycle. These data are in agreement with colorimetric and fluorimetric estimates of 24-h urinary estriol values throughout the menstrual cycle. The perovulatory rise of urinary E 3 -16G excretion, as quantitated by this RIA, is comparable to that of serum estradiol measured in the same 7 women, but peaks 1 to 2 days later than the serum estradiol surge. (author)

  6. Cycle killer... qu'est-ce que c'est? On the comparative approximability of hybridization number and directed feedback vertex set

    NARCIS (Netherlands)

    Kelk, S.M.; Iersel, van L.J.J.; Lekic, N.; Linz, S.; Scornavacca, C.; Stougie, L.

    2011-01-01

    We show that the problem of computing the hybridization number of two rooted binary phylogenetic trees on the same set of taxa X has a constant factor polynomial-time approximation if and only if the problem of computing a minimum-size feedback vertex set in a directed graph (DFVS) has a constant

  7. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  8. Catalytic Organometallic Reactions of Ammonia

    Science.gov (United States)

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  9. 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.

  10. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  11. Sulfur cycle

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.

    Microbes, especially bacteria, play an important role in oxidative and reductive cycle of sulfur. The oxidative part of the cycle is mediated by photosynthetic bacteria in the presence of light energy and chemosynthetic forms in the absence of light...

  12. Redox non-innocent ligands: versatile new tools to control catalytic reactions

    NARCIS (Netherlands)

    Lyaskovskyy, V.; de Bruin, B.

    2012-01-01

    In this (tutorial overview) perspective we highlight the use of "redox non-innocent" ligands in catalysis. Two main types of reactivity in which the redox non-innocent ligand is involved can be specified: (A) The redox active ligand participates in the catalytic cycle only by accepting/donating

  13. SNCR technology for NO sub x reduction in the cement industry. [Selective non-catalytic reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kupper, D; Brentrup, L [Krupp Polysius AG, Beckum (Germany)

    1992-03-01

    This article discusses the selective non-catalytic (SNCR) process for reducing nitrogen oxides in exhaust gases from cement plants. Topics covered include operating experience, injection of additives, selection of the additive, operating costs, reduction efficiency of SNCR, capital expenditure, secondary emissions and cycles of ammonium. (UK).

  14. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  15. Cross-catalytic peptide nucleic acid (PNA) replication based on templated ligation

    DEFF Research Database (Denmark)

    Singhal, Abhishek; Nielsen, Peter E

    2014-01-01

    We report the first PNA self-replicating system based on template directed cross-catalytic ligation, a process analogous to biological replication. Using two template PNAs and four pentameric precursor PNAs, all four possible carbodiimide assisted amide ligation products were detected...... precursors. Cross-catalytic product formation followed product inhibited kinetics, but approximately two replication rounds were observed. Analogous but less efficient replication was found for a similar tetrameric system. These results demonstrate that simpler nucleobase replication systems than natural...

  16. Petrochemical promoters in catalytic cracking

    International Nuclear Information System (INIS)

    Gomez, Maria; Vargas, Clemencia; Lizcano, Javier

    2010-01-01

    This study is based on the current scheme followed by a refinery with available Catalytic Cracking capacity to process new feedstocks such as Straight Run Naphtha and Naphthas from FCC. These feedstocks are of petrochemical interest to produce Ethane, Ethylene, Propylene, i-Butane, Toluene and Xylene. To evaluate the potential of these new streams versus the Cracking-charged Residues, it was performed a detailed chemical analysis on the structural groups in carbons [C1-C12] at the reactor product obtained in pilot plant. A catalyst with and without Propylene Promoter Additive was used. This study analyzes the differences in the chemical composition of the feedstocks, relating them to the yield of each petrochemical product. Straight Run Naphthas with a high content of Naphthenes, and Paraffines n[C5-C12] and i[C7-C12] are selective to the production of i-Butane and Propane, while Naphthas from FCC with a high content of n[C5-C12]Olefins, i-Olefins, and Aromatics are more selective to Propylene, Toluene, and Xylene. Concerning Catalytic Cracking of Naphthas, the Additive has similar selectivity for all the petrochemical products, their yields increase by about one point with 4%wt of Additive, while in cracking of Residues, the Additive increases in three points Propylene yield, corresponding to a selectivity of 50% (?C3= / ?LPG).

  17. Catalytic converters in the fireplace

    International Nuclear Information System (INIS)

    Kouki, J.

    1995-01-01

    In addition to selecting the appropriate means of heating and using dry fuel, the amount of harmful emissions contained by flue gases produced by fireplaces can be reduced by technical means. One such option is to use an oxidising catalytic converter. Tests at TTS Institute's Heating Studies Experimental Station have focused on two such converters (dense and coarse) mounted in light-weight iron heating stoves. The ability of the dense catalytic converter to oxidise carbon monoxide gases proved to be good. The concentration of carbon monoxide in the flue gases was reduced by as much as 90 %. Measurements conducted by VTT (Technical Research Centre of Finland) showed that the conversion of other gases, e.g. of methane, was good. The exhaust resistance caused by the dense converter was so great as to necessitate the mounting of a fluegas evacuation fan in the chimney for the purpose of creating sufficient draught. When relying on natural draught, the dense converter requires a chimney of at least 7 metres and a by-pass connection while the fire is being lit. In addition, the converter will have to be constructed to be less dense and this will mean that it's capability to oxidise non-combusted gases will be reduced. The coarse converter did not impair the draught but it's oxidising property was insufficient. With the tests over, the converter was not observed to have become blocked up by impurities

  18. Mechanisms of catalytic activity in heavily coated hydrocracking catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Millan, M.; Adell, C.; Hinojosa, C.; Herod, A.A.; Kandiyoti, R. [University of London Imperial College Science Technology & Medicine, London (United Kingdom). Dept. of Chemical Engineering

    2008-01-15

    Catalyst deactivation by coke deposition has a direct impact on the economic viability of heavy hydrocarbon upgrading processes, such as coal liquefaction and oil residue hydroprocessing. Coke deposition is responsible for rapid loss of catalytic activity and it mostly takes place in the early stages of hydrocracking. The effect of carbonaceous deposition on the catalytic activity of a chromium pillared montmorillonite has been studied in the present work. Its catalytic activity in hydrocracking a coal extract was evaluated based on the boiling point distributions of feed and products obtained by thermogravimetric analysis (TGA), and their characterisation by size exclusion chromatography (SEC) and UV-Fluorescence spectroscopy (UV-F). A large deposition on the catalyst was observed after two successive 2-hour long runs in which the catalyst recovered from the first run was reused in the second. The pillared clay retained its activity even though it showed high carbon loading, a large drop in surface area and complete apparent pore blockage. Some observations may contribute to explain this persistent catalytic activity. First, there is evidence suggesting the dynamic nature of the carbonaceous deposits, which continuously exchange material with the liquid, allowing catalytic activity to continue. Secondly, Scanning Electron Microscopy (SEM) on the used Cr montmorillonite has shown preferential deposition on some regions of the catalyst, which leaves a fraction of the surface relatively exposed. Finally, evidence from SEM coupled to X-ray microanalysis also suggest that deposits are thinner in areas where the active phase of the catalyst is present in higher concentrations. Hydrogenation on the active sites would make the deposits more soluble in the liquid cleaning of surrounding area from deposits.

  19. Analysis of combustion performance and emission of extended expansion cycle and iEGR for low heat rejection turbocharged direct injection diesel engines

    Directory of Open Access Journals (Sweden)

    Shabir Mohd F.

    2014-01-01

    Full Text Available Increasing thermal efficiency in diesel engines through low heat rejection concept is a feasible technique. In LHR engines the high heat evolution is achieved by insulating the combustion chamber surfaces and coolant side of the cylinder with partially stabilized zirconia of 0.5 mm thickness and the effective utilization of this heat depend on the engine design and operating conditions. To make the LHR engines more suitable for automobile and stationary applications, the extended expansion was introduced by modifying the inlet cam for late closing of intake valve through Miller’s cycle for extended expansion. Through the extended expansion concept the actual work done increases, exhaust blow-down loss reduced and the thermal efficiency of the LHR engine is improved. In LHR engines, the formation of nitric oxide is more, to reduce the nitric oxide emission, the internal EGR is incorporated using modified exhaust cam with secondary lobe. Modifications of gas exchange with internal EGR resulted in decrease in nitric oxide emissions. In this work, the parametric studies were carried out both theoretically and experimentally. The combustion, performance and emission parameters were studied and were found to be satisfactory.

  20. Quantitative and radiological assessment of PYRO-SFR closed fuel cycle against direct disposal of spent nuclear fuel from Korean nuclear power plants

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Muhammad Minhaj; Lee, Suhong; Cheong, Jaehak; Whang, Jooho [Kyunghee University, Seoul (Korea, Republic of)

    2016-12-15

    Calculations have been made to estimate the generation of SNF including Plutonium (Pu) and minor actinides (MAs) from PWR and PHWR NPPs by using the IAEA code Nuclear Fuel Cycle Simulation System (NFCSS) for the period of 2016, 2030 as 12 more NPPs will be added by the year 2029. In order to find the optimize option for SNF management through sustainable use of nuclear energy system and reduce the associated radiological risk, 4 scenarios to burnout the Pu and MAs are analyzed. Estimation for the amount of SNF including major radionuclides has made for the year of 2016, 2030, 2089 and 2109 with an approximate amount of 148,19.65MT, 248,34.6 MT, 41572.23 MT and 61272.24 MT of SNF will be generated respectively. Radioactivity and radiotoxicity is calculated in order to access the radiological risk in terms of ingestion. Four Transmutation strategies is predicted to make Korean NPPs sustainable by incorporating KALIMER-600 (Burner) reactor in Korean nuclear fleet with an approximate transmutation rate of 99.77%, 96.57%, 95.34% and 97.58% for MA only (scenario-1), (MA & Pu) scenario-2, scenario-3 (MA only till the year 2125) and scenario-4 MA & Pu till the year 2148) respectively.

  1. Catalytic strategy used by the myosin motor to hydrolyze ATP.

    Science.gov (United States)

    Kiani, Farooq Ahmad; Fischer, Stefan

    2014-07-22

    Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

  2. 17α-Ethinylestradiol (EE2) treatment of wild roach (Rutilus rutilus) during early life development disrupts expression of genes directly involved in the feedback cycle of estrogen.

    Science.gov (United States)

    Nikoleris, Lina; Hultin, Cecilia L; Hallgren, Per; Hansson, Maria C

    2016-02-01

    Fish are more sensitive to introduced disturbances from synthetic endocrine disrupting compounds during early life phases compared with mature stages. 17α-Ethinylestradiol (EE2), which is the active compound in human oral contraceptives and hormone replacement therapies, is today ever present in the effluents from sewage treatment plants. EE2 targets and interacts with the endogenous biological systems of exposed vertebrates resulting in to large extents unknown short- and long-term effects. We investigated how EE2 exposure affects expression profiles of a large number of target genes during early life of roach (Rutilus rutilus). We exposed fertilized roach eggs collected from a lake in Southern Sweden to EE2 for 12weeks together with 1+-year-old roach in aquaria. We measured the gene expression of the estrogen receptor (esr)1/2a/2b, androgen receptor (ar), vitellogenin, cytochrome P450 (cyp)19a1a/1b in fertilized eggs; newly hatched larvae; 12-week-old fry; and juvenile wild roach (1+-year-old). Results shows that an EE2 concentration as low as 0.5ng/L significantly affects gene expression during early development. Gene expression responses vary both among life stages and molecular receptors. We also show that the gene profile of the estrogen feedback cycle to a large extent depends on the relationship between the three esr genes and the two cyp19a1 genes, which are all up-regulated with age. Results indicate that a disruption of the natural activity of the dominant esr gene could lead to detrimental biological effects if EE2 exposure occurs during development, even if this exposure occurred for only a short period. Copyright © 2015. Published by Elsevier Inc.

  3. Life cycle greenhouse gas emissions impacts of the adoption of the EU Directive on biofuels in Spain. Effect of the import of raw materials and land use changes

    International Nuclear Information System (INIS)

    Lechon, Y.; Cabal, H.; Saez, R.

    2011-01-01

    The objective of this paper is to evaluate the greenhouse gas (GHG) emissions impacts of the use of different alternative biofuels in passenger vehicles in Spain in order to meet EU biofuel goals. Different crop production alternatives are analysed, including the possible import of some raw materials. Availability of land for national production of the raw materials is analysed and indirect land use changes and associated GHG emissions are quantified. There are important differences in GHG emissions of biofuels depending on the raw material used and whether this is domestically produced or imported. Ethanol production using imported cereals and FAME production using domestic rapeseed have the highest GHG emissions per kilometre driven. Fatty acid methyl ester (FAME) production from sunflower has shown the lowest emissions. When taking into account the results of GHG emissions savings per hectare, these findings are somehow reversed. Production of ethanol and around 12% of FAME can be done domestically. The rest will need to be imported and will cause indirect land use change (ILUC). Therefore, ethanol production will not displace any land, whereas FAME production will displace some amounts of land. Calculated ILUC factors are 29%-34%. The additional GHG emissions due to these indirect land use changes are significant (67%-344% of life cycle GHG emissions). Standalone, the EU biofuel targets can have important benefits for Spain in terms of global warming emissions avoided. However, when considering the impact of land use change effects, these benefits are significantly reduced and can even be negative. -- Highlights: → Biofuel greenhouse gas emissions in Spain using domestic and imported raw materials. → Availability of land, indirect land use changes (ILUC) and GHG emissions quantified. → Important differences in biofuels GHG emissions depending on the raw material found. → All ethanol and 12% FAME can be produced domestically with ILUC factors of 29

  4. Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Wei; Zheng, Richard; Brown, Heather; Li, Joanne; Holladay, John; Cooper, Alan; Rao, Tony

    2012-04-13

    This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

  5. Thorium cycles and proliferation

    International Nuclear Information System (INIS)

    Lovins, A.B.

    1979-01-01

    This paper analyzes several prevalent misconceptions about nuclear fuel cycles that breed fissile uranium-233 from thorium. Its main conclusions are: U-233, despite the gamma radioactivity of associated isotopes, is a rather attractive material for making fission bombs, and is a credible material for subnational as well as national groups to use for this purpose; (2) pure thorium cycles, which in effect merely substitute U-233 for Pu, would take many decades and much U to establish, and offer no significant safeguards advantage over Pu, cycles; (3) denatured Th-U cycles, which dilute the U-233 with inert U-238 to a level not directly usable in bombs, are not an effective safeguard even against subnational bomb-making; (4) several other features of mixed Th-U cycles are rather unattractive from a safeguards point of view; (5) thus, Th cycles of any kind are not a technical fix for proliferation (national or subnational) and, though probably more safeguardable than Pu cycles, are less so than once-through U cycles that entail no reprocessing; (6) while thorium cycles have some potential technical advantages, including flexibility, they cannot provide major savings in nuclear fuel resources compared to simpler ways of saving neutrons and U; and (7) while advocates of nuclear power may find Th cycles worth exploring, such cycles do not differ fundamentally from U cycles in any of the respects--including safeguards and fuel resources--that are relevant to the broader nuclear debate, and should not be euphorically embraced as if they did

  6. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

  7. Heterogeneous Photo catalytic Degradation of Hazardous Waste in Aqueous Suspension

    International Nuclear Information System (INIS)

    Sadek, S.A.; Ebraheem, S.; Friesen, K.J.

    1999-01-01

    The photo catalytic degradation of hazardous waste like chlorinated paraffin compound (1,12-Dichlorodoecane Ded) was investigated in different aquatic media using GC-MSD. The direct photolysis of Ded in HPLC water was considered to be negligible (k = 0.0020+-0.0007h - 1 ) . An acceleration of the photodegradation rate was occurred in presence of different TiO 2 catalyst systems. Molecular oxygen was found to play a vital role in the degradation process. Anatase TiO 2 was proved to be the most efficient one (k=0.7670+-0.0876h -1 ), while the rate constant of the rutile TiO 2 was calculated to be 0.2780+-0.0342h -1 . Improvement of photo catalytic efficiency of rutile TiO 2 was achieved by addition of Fe +2 giving a rate constant =0.6710+-0.0786h -1

  8. Outstanding catalytic activity of ultra-pure platinum nanoparticles.

    Science.gov (United States)

    Januszewska, Aneta; Dercz, Grzegorz; Piwowar, Justyna; Jurczakowski, Rafal; Lewera, Adam

    2013-12-09

    Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as-received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as-received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy-harvesting/data-storage devices. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Ultraviolet laser deposition of graphene thin films without catalytic layers

    KAUST Repository

    Sarath Kumar, S. R.

    2013-01-09

    In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

  10. Ultraviolet laser deposition of graphene thin films without catalytic layers

    KAUST Repository

    Sarath Kumar, S. R.; Alshareef, Husam N.

    2013-01-01

    In this letter, the formation of nanostructured graphene by ultraviolet laser ablation of a highly ordered pyrolytic graphite target under optimized conditions is demonstrated, without a catalytic layer, and a model for the growth process is proposed. Previously, graphene film deposition by low-energy laser (2.3 eV) was explained by photo-thermal models, which implied that graphene films cannot be deposited by laser energies higher than the C-C bond energy in highly ordered pyrolytic graphite (3.7 eV). Here, we show that nanostructured graphene films can in fact be deposited using ultraviolet laser (5 eV) directly over different substrates, without a catalytic layer. The formation of graphene is explained by bond-breaking assisted by photoelectronic excitation leading to formation of carbon clusters at the target and annealing out of defects at the substrate.

  11. Catalytic hydrogenation of carbon monoxide

    International Nuclear Information System (INIS)

    Wayland, B.B.

    1993-12-01

    Focus of this project is on developing new approaches for hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. The strategies to accomplish CO reduction are based on favorable thermodynamics manifested by rhodium macrocycles for producing a series of intermediates implicated in the catalytic hydrogenation of CO. Metalloformyl complexes from reactions of H 2 and CO, and CO reductive coupling to form metallo α-diketone species provide alternate routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics are promising candidates for future development

  12. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J; Koljonen, T [VTT Energy, Espoo (Finland)

    1997-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  13. Non-catalytic recuperative reformer

    Science.gov (United States)

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  14. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  15. Solid strong base K-Pt/NaY zeolite nano-catalytic system for completed elimination of formaldehyde at room temperature

    Science.gov (United States)

    Song, Shaoqing; Wu, Xi; Lu, Changhai; Wen, Meicheng; Le, Zhanggao; Jiang, Shujuan

    2018-06-01

    Solid strong base nano-catalytic system of K-modification NaY zeolite supported 0.08% Pt (K-Pt/NaY) were constructed for eliminating HCHO at room temperature. In the catalytic process, activation energy over K-Pt/NaY nano-catalytic system was greatly decreased along with the enhanced reaction rate. Characterization and catalytic tests revealed the surface electron structure of K-Pt/NaY was improved, as reflected by the enhanced HCHO adsorption capability, high sbnd OH concentration, and low-temperature reducibility. Therefore, the optimal K-Pt/NaY showed high catalytic efficiency and strong H2O tolerance for HCHO elimination by directly promoting the reaction between active sbnd OH and formate species. These results may suggest a new way for probing the advanced solid strong base nano-catalytic system for the catalytic elimination of indoor HCHO.

  16. The evolution of catalytic function

    Science.gov (United States)

    Maurel, Marie-Christine; Ricard, Jacques

    2006-03-01

    It is very likely that the main driving force of enzyme evolution is the requirement to improve catalytic and regulatory efficiency which results from the intrinsic performance as well as from the spatial and functional organization of enzymes in living cells. Kinetic co-operativity may occur in simple monomeric proteins if they display “slow” conformational transitions, at the cost of catalytic efficiency. Oligomeric enzymes on the other hand can be both efficient and co-operative. We speculate that the main reason for the emergence of co-operative oligomeric enzymes is the need for catalysts that are both cooperative and efficient. As it is not useful for an enzyme to respond to a change of substrate concentration in a complex kinetic way, the emergence of symmetry has its probable origin in a requirement for “functional simplicity”. In a living cell, enzyme are associated with other macromolecules and membranes. The fine tuning of their activity may also be reached through mutations of the microenvironment. Our hypothesis is that these mutations are related to the vectorial transport of molecules, to achieve the hysteresis loops of enzyme reactions generated by the coupling of reaction and diffusion, through the co-operativity brought about by electric interactions between a charged substrate and a membrane, and last but not least, through oscillations. As the physical origins of these effects are very simple and do not require complex molecular devices, it is very likely that the functional advantage generated by the spatial and functional organization of enzyme molecules within the cell have appeared in prebiotic catalysis or very early during the primeval stages of biological evolution. We shall began this paper by presenting the nature of the probable earliest catalysts in the RNA world.

  17. High-efficiency plasma catalytic removal of dilute benzene from air

    International Nuclear Information System (INIS)

    Fan, Hong-Yu; Shi, Chuan; Li, Xiao-Song; Zhao, De-Zhi; Xu, Yong; Zhu, Ai-Min

    2009-01-01

    Achieving complete oxidation, good humidity tolerance and low energy cost is the key issue that needs to be addressed in plasma catalytic volatile organic compounds removal from air. For this purpose, Ag/HZSM-5 catalyst-packed dielectric barrier discharge using a cycled system composed of a storage stage and a discharge stage was studied. For dilute benzene removal from simulated air, Ag/HZSM-5 catalysts exhibit not only preferential adsorption of benzene in humid air at the storage stage but also almost complete oxidation of adsorbed benzene at the discharge stage. Five 'storage-discharge' cycles were examined, which suggests that Ag/HZSM-5 catalysts are very stable during the cycled 'storage-discharge' (CSD) plasma catalytic process. High oxidation rate of absorbed benzene as well as low energy cost can be achieved at a moderate discharge power. In an example of the CSD plasma catalytic remedy of simulated air containing 4.7 ppm benzene with 50% RH and 600 ml min -1 flow rate, the energy cost was as low as 3.7 x 10 -3 kWh m -3 air. This extremely low energy cost to remove low-concentration pollutants from air undoubtedly makes the environmental applications of the plasma catalytic technique practical.

  18. Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

    International Nuclear Information System (INIS)

    Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai; Suriye, Kongkiat; Nonkhamwong, Anuwat

    2013-01-01

    We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed

  19. Catalytic performance improvement of styrene hydrogenation in trickle bed reactor by using periodic operation

    Energy Technology Data Exchange (ETDEWEB)

    Wongkia, Atittahn; Praserthdam, Piyasan; Assabumrungrat, Suttichai [Chulalongkorn University, Bangkok (Thailand); Suriye, Kongkiat; Nonkhamwong, Anuwat [SCG Chemicals Co. Ltd., Bangkok (Thailand)

    2013-03-15

    We investigated the catalytic performance improvement of styrene hydrogenation in a trickle bed reactor by using periodic operation. The effects of cycle period and split on relative conversion, which is defined as styrene conversion obtained from periodic operation over that from steady state operation, were examined at various operating conditions including gas and average liquid flow rates, pressure and temperature. The experimental results reveal that both cycle period and split have strong influence on the catalytic performance. The fast mode (short cycle period) is a favorable condition. The improvement by the periodic operation becomes less pronounced for operations at high average liquid flow rate, pressure and temperature. From this study, a maximum improvement of styrene conversion of 18% is observed.

  20. Catalytic modification of cellulose and hemicellulose - Sugarefine

    Energy Technology Data Exchange (ETDEWEB)

    Repo, T. [Helsinki Univ. (Finland),Laboratory of Inorganic Chemistry], email: timo.repo@helsinki.fi

    2012-07-01

    The main goal of the project is to develop catalytic methods for the modification of lignocellulose-based saccharides in the biorefineries. The products of these reactions could be used for example as biofuel components, raw materials for the chemical industry, solvents and precursors for biopolymers. The catalyst development aims at creating efficient, selective and green catalytic methods for profitable use in biorefineries. The project is divided in three work packages: In WP1 (Catalytic dehydration of cellulose) the aim is at developing non-toxic, efficient methods for the catalytic dehydration of cellulose the target molecule being here 5-hydroxymethylfurfural (5-HMF). 5-HMF is an interesting platform chemical for the production of fuel additives, solvents and polymers. In WP2 (Catalytic reduction), the objective of the catalytic reduction studies is to produce commercially interesting monofunctional chemicals, such as 1-butanol or 2-methyltetrahydrofuran (2-MeTHF). In WP3 (Catalytic oxidation), the research focuses on developing a green and efficient oxidation method for producing acids. Whereas acetic and formic acids are bulk chemicals, diacids such as glucaric and xylaric acids are valuable specialty chemicals for detergent, polymer and food production.

  1. Additive Manufacturing of Catalytically Active Living Materials.

    Science.gov (United States)

    Saha, Abhijit; Johnston, Trevor G; Shafranek, Ryan T; Goodman, Cassandra J; Zalatan, Jesse G; Storti, Duane W; Ganter, Mark A; Nelson, Alshakim

    2018-04-25

    Living materials, which are composites of living cells residing in a polymeric matrix, are designed to utilize the innate functionalities of the cells to address a broad range of applications such as fermentation and biosensing. Herein, we demonstrate the additive manufacturing of catalytically active living materials (AMCALM) for continuous fermentation. A multi-stimuli-responsive yeast-laden hydrogel ink, based on F127-dimethacrylate, was developed and printed using a direct-write 3D printer. The reversible stimuli-responsive behaviors of the polymer hydrogel inks to temperature and pressure are critical, as they enabled the facile incorporation of yeast cells and subsequent fabrication of 3D lattice constructs. Subsequent photo-cross-linking of the printed polymer hydrogel afforded a robust elastic material. These yeast-laden living materials were metabolically active in the fermentation of glucose into ethanol for 2 weeks in a continuous batch process without significant reduction in efficiency (∼90% yield of ethanol). This cell immobilization platform may potentially be applicable toward other genetically modified yeast strains to produce other high-value chemicals in a continuous biofermentation process.

  2. Catalytic Wittig and aza-Wittig reactions

    Directory of Open Access Journals (Sweden)

    Zhiqi Lao

    2016-11-01

    Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

  3. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens

    2015-01-01

    of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social......The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...

  4. Efficient catalytic combustion in integrated micropellistors

    International Nuclear Information System (INIS)

    Bársony, I; Ádám, M; Fürjes, P; Dücső, Cs; Lucklum, R; Hirschfelder, M; Kulinyi, S

    2009-01-01

    This paper analyses two of the key issues of the development of catalytic combustion-type sensors: the selection and production of active catalytic particles on the micropellistor surface as well as the realization of a reliable thermal conduction between heater element and catalytic surface, for the sensing of temperature increase produced by the combustion. The report also demonstrates that chemical sensor product development by a MEMS process is a continuous struggle for elimination of all uncertainties influencing reliability and sensitivity of the final product

  5. Key parameters controlling the performance of catalytic motors

    Energy Technology Data Exchange (ETDEWEB)

    Esplandiu, Maria J.; Afshar Farniya, Ali [Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona (Spain); Reguera, David, E-mail: dreguera@ub.edu [Departament de Física Fonamental, Universitat de Barcelona, C/Martí i Franquès 1, 08028 Barcelona (Spain)

    2016-03-28

    The development of autonomous micro/nanomotors driven by self-generated chemical gradients is a topic of high interest given their potential impact in medicine and environmental remediation. Although impressive functionalities of these devices have been demonstrated, a detailed understanding of the propulsion mechanism is still lacking. In this work, we perform a comprehensive numerical analysis of the key parameters governing the actuation of bimetallic catalytic micropumps. We show that the fluid motion is driven by self-generated electro-osmosis where the electric field originates by a proton current rather than by a lateral charge asymmetry inside the double layer. Hence, the surface potential and the electric field are the key parameters for setting the pumping strength and directionality. The proton flux that generates the electric field stems from the proton gradient induced by the electrochemical reactions taken place at the pump. Surprisingly the electric field and consequently the fluid flow are mainly controlled by the ionic strength and not by the conductivity of the solution, as one could have expected. We have also analyzed the influence of the chemical fuel concentration, electrochemical reaction rates, and size of the metallic structures for an optimized pump performance. Our findings cast light on the complex chemomechanical actuation of catalytic motors and provide important clues for the search, design, and optimization of novel catalytic actuators.

  6. Optical manipulation and catalytic activity enhanced by surface plasmon effect

    Science.gov (United States)

    Zou, Ningmu; Min, Jiang; Jiao, Wenxiang; Wang, Guanghui

    2017-02-01

    For optical manipulation, a nano-optical conveyor belt consisting of an array of gold plasmonic non-concentric nano-rings (PNNRs) is demonstrated for the realization of trapping and unidirectional transportation of nanoparticles by polarization rotation of excitation beam. These hot spots of an asymmetric plasmonic nanostructure are polarization dependent, therefore, one can use the incident polarization state to manipulate the trapped targets. Trapped particles could be transferred between adjacent PNNRs in a given direction just by rotating the polarization of incident beam due to unbalanced potential. The angular dependent distribution of electric field around PNNR has been solved using the three- dimensional finite-difference time-domain (FDTD) technique. For optical enhanced catalytic activity, the spectral properties of dimers of Au nanorod-Au nanorod nanostructures under the excitation of 532nm photons have been investigated. With a super-resolution catalytic mapping technique, we identified the existence of "hot spot" in terms of catalytic reactivity at the gap region within the twined plasmonic nanostructure. Also, FDTD calculation has revealed an intrinsic correlation between hot electron transfer.

  7. Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

    Directory of Open Access Journals (Sweden)

    Rotcharin Sawisai

    2017-01-01

    Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

  8. Vacuum-insulated catalytic converter

    Science.gov (United States)

    Benson, David K.

    2001-01-01

    A catalytic converter has an inner canister that contains catalyst-coated substrates and an outer canister that encloses an annular, variable vacuum insulation chamber surrounding the inner canister. An annular tank containing phase-change material for heat storage and release is positioned in the variable vacuum insulation chamber a distance spaced part from the inner canister. A reversible hydrogen getter in the variable vacuum insulation chamber, preferably on a surface of the heat storage tank, releases hydrogen into the variable vacuum insulation chamber to conduct heat when the phase-change material is hot and absorbs the hydrogen to limit heat transfer to radiation when the phase-change material is cool. A porous zeolite trap in the inner canister absorbs and retains hydrocarbons from the exhaust gases when the catalyst-coated substrates and zeolite trap are cold and releases the hydrocarbons for reaction on the catalyst-coated substrate when the zeolite trap and catalyst-coated substrate get hot.

  9. Catalytic hydrotreatment of refinery waste

    Energy Technology Data Exchange (ETDEWEB)

    1989-01-01

    The object of the project is to produce liquid hydrocarbons by the catalytic hydroprocessing of solid refinery wastes (hard pitches) in order to improve the profitability of deep conversion processes and reduce the excess production of heavy fuels. The project was mostly carried out on the ASVAHL demonstration platform site, at Solaize, and hard pitches were produced primarily by deasphalting of atmospheric or vacuum distillation residues. The project includes two experimental phases and an economic evaluation study phase. In phase 1, two granular catalysts were used to transform pitch into standard low sulphur fuel oil: a continuously moving bed, with demetallation and conversion catalyst; a fixed bed, with hydrorefining catalyst. In phase 2 of the project, it was proven that a hydrotreatment process using a finely dispersed catalyst in the feedstock, can, under realistic operating conditions, transform with goods yields hard pitch into distillates that can be refined through standard methods. In phase 3 of the project, it was shown that the economics of such processes are tightly linked to the price differential between white and black oil products, which is expected to increase in the future. Furthermore, the evolution of environmental constraints will impel the use of such methods, thus avoiding the coproduction of polluting solid residues.

  10. Chemistry and engineering of catalytic hydrodesulfurization

    NARCIS (Netherlands)

    Schuit, G.C.A.; Gates, B.C.

    1973-01-01

    A review with 74 refs. on catalytic hydrodesulfurization of pure compds. and petroleum feedstocks, with emphasis on reaction intermediates and structures of Al2O3-supported Ni-W and Co-Mo catalysts. [on SciFinder (R)

  11. Glacial cycles

    DEFF Research Database (Denmark)

    Kaufmann, R. K.; Juselius, Katarina

    We use a statistical model, the cointegrated vector autoregressive model, to assess the degree to which variations in Earth's orbit and endogenous climate dynamics can be used to simulate glacial cycles during the late Quaternary (390 kyr-present). To do so, we estimate models of varying complexity...... and compare the accuracy of their in-sample simulations. Results indicate that strong statistical associations between endogenous climate variables are not enough for statistical models to reproduce glacial cycles. Rather, changes in solar insolation associated with changes in Earth's orbit are needed...... to simulate glacial cycles accurately. Also, results suggest that non-linear 10 dynamics, threshold effects, and/or free oscillations may not play an overriding role in glacial cycles....

  12. Fuel cycles

    International Nuclear Information System (INIS)

    Hawley, N.J.

    1983-05-01

    AECL publications, from the open literature, on fuels and fuel cycles used in CANDU reactors are listed in this bibliography. The accompanying index is by subject. The bibliography will be brought up to date periodically

  13. Catalytic Aminohalogenation of Alkenes and Alkynes.

    Science.gov (United States)

    Chemler, Sherry R; Bovino, Michael T

    2013-06-07

    Catalytic aminohalogenation methods enable the regio- and stereoselective vicinal difunctionalization of alkynes, allenes and alkenes with amine and halogen moieties. A range of protocols and reaction mechanisms including organometallic, Lewis base, Lewis acid and Brønsted acid catalysis have been disclosed, enabling the regio- and stereoselective synthesis of halogen-functionalized acyclic amines and nitrogen heterocycles. Recent advances including aminofluorination and catalytic enantioselective aminohalogenation reactions are summarized in this review.

  14. Kinetic catalytic studies of scorpion's hemocyanin

    International Nuclear Information System (INIS)

    Queinnec, E.; Vuillaume, M.; Gardes-Albert, M.; Ferradini, C.; Ducancel, F.

    1991-01-01

    Hemocyanins are copper proteins which function as oxygen carriers in the haemolymph of Molluscs and Arthropods. They possess enzymatic properties: peroxidatic and catalatic activities, although they have neither iron nor porphyrin ring at the active site. The kinetics of the catalytic reaction is described. The reaction of superoxide anion with hemocyanin has been studied using pulse radiolysis at pH 9. The catalytic rate constant is 3.5 X 10 7 mol -1 .l.s -1 [fr

  15. In situ catalytic growth of large-area multilayered graphene/MoS2 heterostructures

    Science.gov (United States)

    Fu, Wei; Du, Fei-Hu; Su, Juan; Li, Xin-Hao; Wei, Xiao; Ye, Tian-Nan; Wang, Kai-Xue; Chen, Jie-Sheng

    2014-04-01

    Stacking various two-dimensional atomic crystals on top of each other is a feasible approach to create unique multilayered heterostructures with desired properties. Herein for the first time, we present a controlled preparation of large-area graphene/MoS2 heterostructures via a simple heating procedure on Mo-oleate complex coated sodium sulfate under N2 atmosphere. Through a direct in situ catalytic reaction, graphene layer has been uniformly grown on the MoS2 film formed by the reaction of Mo species with S pecies, which is from the carbothermal reduction of sodium sulfate. Due to the excellent graphene ``painting'' on MoS2 atomic layers, the significantly shortened lithium ion diffusion distance and the markedly enhanced electronic conductivity, these multilayered graphene/MoS2 heterostructures exhibit high specific capacity, unprecedented rate performance and outstanding cycling stability, especially at a high current density, when used as an anode material for lithium batteries. This work provides a simple but efficient route for the controlled fabrication of large-area multilayered graphene/metal sulfide heterostructures with promising applications in battery manufacture, electronics or catalysis.

  16. Fuel rich and fuel lean catalytic combustion of the stabilized confined turbulent gaseous diffusion flames over noble metal disc burners

    Directory of Open Access Journals (Sweden)

    Amal S. Zakhary

    2014-03-01

    Full Text Available Catalytic combustion of stabilized confined turbulent gaseous diffusion flames using Pt/Al2O3 and Pd/Al2O3 disc burners situated in the combustion domain under both fuel-rich and fuel-lean conditions was experimentally studied. Commercial LPG fuel having an average composition of: 23% propane, 76% butane, and 1% pentane was used. The thermal structure of these catalytic flames developed over Pt/Al2O3 and Pd/Al2O3 burners were examined via measuring the mean temperature distribution in the radial direction at different axial locations along the flames. Under-fuel-rich condition the flames operated over Pt catalytic disc attained high temperature values in order to express the progress of combustion and were found to achieve higher activity as compared to the flames developed over Pd catalytic disc. These two types of catalytic flames demonstrated an increase in the reaction rate with the downstream axial distance and hence, an increase in the flame temperatures was associated with partial oxidation towards CO due to the lack of oxygen. However, under fuel-lean conditions the catalytic flame over Pd catalyst recorded comparatively higher temperatures within the flame core in the near region of the main reaction zone than over Pt disc burner. These two catalytic flames over Pt and Pd disc burners showed complete oxidation to CO2 since the catalytic surface is covered by more rich oxygen under the fuel-lean condition.

  17. Culture in cycles: considering H.T. Odum's 'information cycle'

    Science.gov (United States)

    Abel, Thomas

    2014-01-01

    'Culture' remains a conundrum in anthropology. When recast in the mold of 'information cycles,' culture is transformed. New fault lines appear. Information is splintered into parallel or nested forms. Dynamics becomes cycling. Energy is essential. And culture has function in a directional universe. The 'information cycle' is the crowning component of H.T. Odum's theory of general systems. What follows is an application of the information cycle to the cultural domains of discourse, social media, ritual, education, journalism, technology, academia, and law, which were never attempted by Odum. In information cycles, cultural information is perpetuated - maintained against Second Law depreciation. Conclusions are that culture is in fact a nested hierarchy of cultural forms. Each scale of information production is semi-autonomous, with its own evolutionary dynamics of production and selection in an information cycle. Simultaneously, each information cycle is channeled or entrained by its larger scale of information and ultimately human-ecosystem structuring.

  18. Adsorbent catalytic nanoparticles and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-01-31

    The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

  19. Cytochromes P450: History, Classes, Catalytic Mechanism, and Industrial Application.

    Science.gov (United States)

    Cook, D J; Finnigan, J D; Cook, K; Black, G W; Charnock, S J

    Cytochromes P450, a family of heme-containing monooxygenases that catalyze a diverse range of oxidative reactions, are so-called due to their maximum absorbance at 450nm, ie, "Pigment-450nm," when bound to carbon monoxide. They have appeal both academically and commercially due to their high degree of regio- and stereoselectivity, for example, in the area of active pharmaceutical ingredient synthesis. Despite this potential, they often exhibit poor stability, low turnover numbers and typically require electron transport protein(s) for catalysis. P450 systems exist in a variety of functional domain architectures, organized into 10 classes. P450s are also divided into families, each of which is based solely on amino acid sequence homology. Their catalytic mechanism employs a very complex, multistep catalytic cycle involving a range of transient intermediates. Mutagenesis is a powerful tool for the development of improved biocatalysts and has been used extensively with the archetypal Class VIII P450, BM3, from Bacillus megaterium, but with the increasing scale of genomic sequencing, a huge resource is now available for the discovery of novel P450s. © 2016 Elsevier Inc. All rights reserved.

  20. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U. J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A. M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  1. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption – Catalytic wet air oxidation on activated carbons

    International Nuclear Information System (INIS)

    Quesada-Peñate, I.; Julcour-Lebigue, C.; Jáuregui-Haza, U.J.; Wilhelm, A.M.; Delmas, H.

    2012-01-01

    Highlights: ► Three activated carbons (AC) compared as adsorbents and oxidation catalysts. ► Similar evolution for catalytic and adsorptive properties of AC over reuses. ► Acidic and mesoporous AC to be preferred, despite lower initial efficiency. ► Oxidative degradation of paracetamol improves biodegradability. ► Convenient hybrid adsorption–regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

  2. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    details the catalytic partial oxidation of glycerol without preheat: droplets of glycerol are sprayed directly onto the top of the catalyst bed, where they react autothermally with contact times on the order of tau ≈ 30 ms. The reactive flash volatilization of glycerol results in equilibrium syngas production over Rh-Ce catalysts. In addition, water can be added to the liquid glycerol, resulting in true autothermal reforming. This highly efficient process can increase H2 yields and alter the H2 to CO ratio, allowing for flexibility in syngas quality depending on the purpose. Chapter 5 details the results of a time on stream experiment, in which optimal syngas conditions are chosen. Although conversion is 100% for 450 hours, these experiments demonstrate the deactivation of the catalyst over time. Deactivation is exhibited by decreases in H2 and CO 2 production accompanied by a steady increase in CO and temperature. These results are explained as a loss of water-gas shift equilibration. SEM images suggest catalyst sintering may play a role; EDS indicates the presence of impurities on the catalyst. In addition, the instability of quartz in the reactor is demonstrated by etching, resulting in a hole in the reactor tube at the end of the experiment. These results suggest prevaporization may be desirable in this application, and that quartz is not a suitable material for the reactive flash volatilization of oxygenated fuels. In Chapter 6, pyrolysis oil samples from three sources - poplar, pine, and hardwoods - are explored in the context of catalytic partial oxidation. Lessons derived from the tests with model compounds are applied to reactor design, resulting in the reactive flash vaporization of bio oils. Syngas is successfully produced, though deactivation due to coke and ash deposition keeps H2 below equlibrium. Coke formation is observed on the reactor walls, but is avoided between the fuel injection site and catalyst by increasing the proximity of these in the reactor

  3. A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia

    DEFF Research Database (Denmark)

    Janssens, Ton V.W.; Falsig, Hanne; Lundegaard, Lars Fahl

    2015-01-01

    For the first time, the standard and fast selective catalytic reduction of NO by NH3 are described in a complete catalytic cycle, that is able to produce the correct stoichiometry, while only allowing adsorption and desorption of stable molecules. The standard SCR reaction is a coupling of the ac...... for standard SCR. Finally, the role of a nitrate/nitrite equilibrium and the possible in uence of Cu dimers and Brønsted sites are discussed, and an explanation is offered as to how a catalyst can be effective for SCR, while being a poor catalyst for NO oxidation to NO2....... spectroscopy (FTIR). A consequence of the reaction scheme is that all intermediates in fast SCR are also part of the standard SCR cycle. The calculated activation energy by density functional theory (DFT) indicates that the oxidation of an NO molecule by O2 to a bidentate nitrate ligand is rate determining...

  4. Credit cycles and macro fundamentals

    NARCIS (Netherlands)

    Koopman, S.J.; Kraeussl, R.G.W.; Lucas, A.; Monteiro, A.

    2009-01-01

    We use an intensity-based framework to study the relation between macroeconomic fundamentals and cycles in defaults and rating activity. Using Standard and Poor's U.S. corporate rating transition and default data over the period 1980-2005, we directly estimate the default and rating cycle from micro

  5. Contributions to the theory of catalytic titrations-III Neutralization catalytic titrations.

    Science.gov (United States)

    Gaál, F F; Abramović, B F

    1985-07-01

    Neutralization catalytic titrations of weak monoprotic adds and bases with both volumetric and coulometric addition of the titrant (strong base/acid) have been simulated by taking into account the equilibrium concentration of the catalyst during the titration. The influence of several factors on the shape of the simulated catalytic titration curve has been investigated and is discussed.

  6. Spectromicroscopy of catalytic relevant processes with sub-micron resolution

    International Nuclear Information System (INIS)

    Guenther, S.; Esch, F.; Gregoratti, L.; Marsi, M.; Kiskinova, M.; Schubert, U. A.; Grotz, P.; Knoezinger, H.; Taglauer, E.; Schuetz, E.; Schaak, A.; Imbihl, R.

    2000-01-01

    The capabilities of the Scanning Photo Electron Microscope (SPEM) at ELETTRA as a unique probing tool in the field of catalysis and surface science are illustrated presenting results of two recent investigations. The lateral resolution and the high surface sensitivity of the SPEM has enabled imaging the initial steps of the spreading processes of MoO 3 crystals on an alumina support surface, a model system of a catalyst used in petrochemistry. In the second study the local adsorbate coverage inside a pulse of a chemical wave occurring in the catalytic NO+H 2 reaction on a Rh(110) single crystal surface has been determined. The microscope was used to monitor the sample surface in situ during the reaction and thus characterizing a temporal and spatial inhomogeneous system. The so-called excitation cycle of the pulse formation has been verified and the adsorbate gradient inside a chemical wave was measured

  7. Highly Efficient Catalytic Cyclic Carbonate Formation by Pyridyl Salicylimines.

    Science.gov (United States)

    Subramanian, Saravanan; Park, Joonho; Byun, Jeehye; Jung, Yousung; Yavuz, Cafer T

    2018-03-21

    Cyclic carbonates as industrial commodities offer a viable nonredox carbon dioxide fixation, and suitable heterogeneous catalysts are vital for their widespread implementation. Here, we report a highly efficient heterogeneous catalyst for CO 2 addition to epoxides based on a newly identified active catalytic pocket consisting of pyridine, imine, and phenol moieties. The polymeric, metal-free catalyst derived from this active site converts less-reactive styrene oxide under atmospheric pressure in quantitative yield and selectivity to the corresponding carbonate. The catalyst does not need additives, solvents, metals, or co-catalysts, can be reused at least 10 cycles without the loss of activity, and scaled up easily to a kilogram scale. Density functional theory calculations reveal that the nucleophilicity of pyridine base gets stronger due to the conjugated imines and H-bonding from phenol accelerates the reaction forward by stabilizing the intermediate.

  8. Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons.

    Science.gov (United States)

    Quesada-Peñate, I; Julcour-Lebigue, C; Jáuregui-Haza, U J; Wilhelm, A M; Delmas, H

    2012-06-30

    The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  10. Coordination cycles

    Czech Academy of Sciences Publication Activity Database

    Steiner, Jakub

    -, č. 274 (2005), s. 1-26 ISSN 1211-3298 Institutional research plan: CEZ:AV0Z70850503 Keywords : coordination * crises * cycles and fluctuations Subject RIV: AH - Economics http://www.cerge-ei.cz/pdf/wp/Wp274.pdf

  11. Happy Cycling

    DEFF Research Database (Denmark)

    Geert Jensen, Birgitte; Nielsen, Tom

    2013-01-01

    og Interaktions Design, Aarhus Universitet under opgave teamet: ”Happy Cycling City – Aarhus”. Udfordringen i studieopgaven var at vise nye attraktive løsningsmuligheder i forhold til cyklens og cyklismens integration i byrum samt at påpege relationen mellem design og overordnede diskussioner af...

  12. Coordination cycles

    Czech Academy of Sciences Publication Activity Database

    Steiner, Jakub

    2008-01-01

    Roč. 63, č. 1 (2008), s. 308-327 ISSN 0899-8256 Institutional research plan: CEZ:AV0Z70850503 Keywords : global games * coordination * crises * cycles and fluctuations Subject RIV: AH - Economics Impact factor: 1.333, year: 2008

  13. Advanced-ORIENT cycle, its scientific progress and prospect for engineering feasibility

    International Nuclear Information System (INIS)

    Koyama, Shin-ichi; Yamagishi, Isao; Fujii, Yasuhiko; Suzuki, Tatsuya; Ozawa, Masaki; Fujita, Reiko; Okada, Ken; Tatenuma, Katsuyoshi; Mimura, Hitoshi

    2011-01-01

    For the ultimate minimization of the ecological risks originated in nuclear fuel recycling, a new fuel cycle paradigm was proposed and the basic researches have been carried out as a first phase under the Adv.-ORIENT (Advanced Optimization by Recycling Instructive Elements) Cycle project. In this paradigm, effective separation of actinide (An) and long lived-fission product (LLFP), transmutation of An, utilization of separated nuclides, such as lanthanides (Lns) and platinum group metals (PGM), were the main directions. In such directions, tertiary pyridine-type resin (TPR) enabled to separate minor actinide (MA)/Ln and then Am/Cm precisely from spent fuel, provided permitting to use HCl as well as and HNO 3 media. Recovery of very pure Am and Cm products could be done in this phase. The PGM and Tc separation; Catalytic electrolytic extraction (CEE) method could effectively separate the light PGM ,Tc from HCl and HNO 3 media, especially by HCl media. The PGM and Tc utilization; Mixed deposit obtained from the CEE experiments, Ru/Rh/Pd/Tc(Re)-Pt electrodes indicated the highest catalytic reactivity on electrolytic production of hydrogen in an alkali solution. Recovery of Cs from simulated spent fuel solution by silica gel loaded with ammonium molybdophosphate (AMP) was carried out, and the uptake rate achieved more than 90%. Separated Cs is expected to utilize as a heat source element. As basic engineering research efforts, some candidate metals, such as Ta, Nb, Zr and Hastelloy-B (Ni-28Mo), were examined to confirm an anti-corrosive property in wide HCl environment. Gram scale experiment to identify a thermo-chemical stability of TPR and TBP (as a reference) was also performed experimentally, and process safety conditions could be found out for its practical use. In this paper, study for each integrant technology was concluded as first trial of Adv.-ORIENT Cycle project, and the perspective for next phase was proposed. (author)

  14. Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

    Science.gov (United States)

    Bandini, Marco; Tragni, Michele

    2009-04-21

    The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

  15. Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

    Science.gov (United States)

    Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

    2010-01-01

    A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

  16. Catalytic microcontact printing without ink

    NARCIS (Netherlands)

    Li, X.; Péter, M.; Huskens, Jurriaan; Reinhoudt, David

    2003-01-01

    A novel microcontact printing technique is described that does not require ink. Patterns were created by direct contact of oxidized PDMS stamps with silyl ether-derivatized, acid-labile SAMs on gold. The surface of the stamps was oxidized by oxygen plasma to give a layer of silicon oxide. These

  17. Fuel cycle based safeguards

    International Nuclear Information System (INIS)

    De Montmollin, J.M.; Higinbotham, W.A.; Gupta, D.

    1985-07-01

    In NPT safeguards the same model approach and absolute-quantity inspection goals are applied at present to all similar facilities, irrespective of the State's fuel cycle. There is a continuing interest and activity on the part of the IAEA in new NPT safeguards approaches that more directly address a State's nuclear activities as a whole. This fuel cycle based safeguards system is expected to a) provide a statement of findings for the entire State rather than only for individual facilities; b) allocate inspection efforts so as to reflect more realistically the different categories of nuclear materials in the different parts of the fuel cycle and c) provide more timely and better coordinated information on the inputs, outputs and inventories of nuclear materials in a State. (orig./RF) [de

  18. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh M; Bragin, O V

    1978-01-01

    A comprehensive review of 1976 Soviet research on catalysis delivered to the 1977 annual session of the USSR Academy of Science Council on Catalysis (Baku 6/16-20/77) covers hydrocarbon reactions, including hydrogenation and hydrogenolysis, dehydrogenation, olefin dimerization and disproportionation, and cyclization and dehydrocyclization (e.g., piperylene cyclization and ethylene cyclotrimerization); catalytic and physicochemical properties of zeolites, including cracking, dehydrogenation, and hydroisomerization catalytic syntheses and conversion of heterocyclic and functional hydrocarbon derivatives, including partial and total oxidation (e.g., of o-xylene to phthalic anhydride); syntheses of thiophenes from alkanes and hydrogen sulfide over certain dehydrogenation catalysts; catalytic syntheses involving carbon oxides ( e.g., the development of a new heterogeneous catalyst for hydroformylation of olefins), and of Co-MgO zeolitic catalysts for synthesis of aliphatic hydrocarbons from carbon dioxide and hydrogen, and fabrication of high-viscosity lubricating oils over bifunctional aluminosilicate catalysts.

  19. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  20. Modeling and simulation of heterogeneous catalytic processes

    CERN Document Server

    Dixon, Anthony

    2014-01-01

    Heterogeneous catalysis and mathematical modeling are essential components of the continuing search for better utilization of raw materials and energy, with reduced impact on the environment. Numerical modeling of chemical systems has progressed rapidly due to increases in computer power, and is used extensively for analysis, design and development of catalytic reactors and processes. This book presents reviews of the state-of-the-art in modeling of heterogeneous catalytic reactors and processes. Reviews by leading authorities in the respective areas Up-to-date reviews of latest techniques in modeling of catalytic processes Mix of US and European authors, as well as academic/industrial/research institute perspectives Connections between computation and experimental methods in some of the chapters.

  1. A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

    Science.gov (United States)

    Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

    2017-11-01

    The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

  2. Catalytic Kinetic Resolution of Biaryl Compounds.

    Science.gov (United States)

    Ma, Gaoyuan; Sibi, Mukund P

    2015-08-10

    Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Thermal and catalytic pyrolysis of plastic waste

    Directory of Open Access Journals (Sweden)

    Débora Almeida

    2016-02-01

    Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

  4. Janus droplet as a catalytic micromotor

    Science.gov (United States)

    Shklyaev, Sergey

    2015-06-01

    Self-propulsion of a Janus droplet in a solution of surfactant, which reacts on a half of a drop surface, is studied theoretically. The droplet acts as a catalytic motor creating a concentration gradient, which generates its surface-tension-driven motion; the self-propulsion speed is rather high, 60 μ \\text{m/s} and more. This catalytic motor has several advantages over other micromotors: simple manufacturing, easily attained neutral buoyancy. In contrast to a single-fluid droplet, which demonstrates a self-propulsion as a result of symmetry breaking instability, for the Janus one no stability threshold exists; hence, the droplet radius can be scaled down to micrometers.

  5. Catalytic burners in larger boiler appliances

    Energy Technology Data Exchange (ETDEWEB)

    Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))

    2009-02-15

    This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

  6. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)

    2012-07-01

    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  7. Using electron beams to investigate catalytic materials

    International Nuclear Information System (INIS)

    Zhang, Bingsen; Su, Dang Sheng

    2014-01-01

    Transmission Electron microscopy (TEM) enables us, not only to reveal the morphology, but also to provide structural, chemical and electronic information about solid catalysts at the atomic level, providing a dramatic driving force for the development of heterogeneous catalysis. Almost all catalytic materials have been studied with TEM in order to obtain information about their structures, which can help us to establish the synthesis-structure-property relationships and to design catalysts with new structures and desired properties. Herein, several examples will be reviewed to illustrate the investigation of catalytic materials by using electron beams. (authors)

  8. Partial catalytic oxidation of CH{sub 4} to synthesis gas for power generation - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Mantzaras, I.; Schneider, A.

    2006-03-15

    The partial oxidation of methane to synthesis gas over rhodium catalysts has been investigated experimentally and numerically in the pressure range of 4 to 10 bar. The methane/oxidizer feed has been diluted with large amounts of H{sub 2}O and CO{sub 2} (up to 70% vol.) in order to simulate new power generation cycles with large exhaust gas recycle. Experiments were carried out in an optically accessible channel-flow reactor that facilitated laser-based in situ measurements, and also in a subscale gas-turbine catalytic reactor. Full-elliptic steady and transient two-dimensional numerical codes were used, which included elementary hetero-/homogeneous chemical reaction schemes. The following are the key conclusions: a) Heterogeneous (catalytic) and homogeneous (gas-phase) schemes have been validated for the partial catalytic oxidation of methane with large exhaust gas recycle. b) The impact of added H{sub 2}O and CO{sub 2} has been elucidated. The added H{sub 2}O increased the methane conversion and hydrogen selectivity, while it decreased the CO selectivity. The chemical impact of CO{sub 2} (dry reforming) was minimal. c) The numerical model reproduced the measured catalytic ignition times. It was further shown that the chemical impact of H{sub 2}O and CO{sub 2} on the catalytic ignition delay times was minimal. d) The noble metal dispersion increased with different support materials, in the order Rh/{alpha}-Al{sub 2}O{sub 3}, Rh/ZrO{sub 2}, and Rh/Ce-ZrO{sub 2}. An evident relationship was established between the noble metal dispersion and the catalytic behavior. (authors)

  9. Fuel cycle

    International Nuclear Information System (INIS)

    Bahm, W.

    1989-01-01

    The situation of the nuclear fuel cycle for LWR type reactors in France and in the Federal Republic of Germany was presented in 14 lectures with the aim to compare the state-of-the-art in both countries. In addition to the momentarily changing fuilds of fuel element development and fueling strategies, the situation of reprocessing, made interesting by some recent developmnts, was portrayed and differences in ultimate waste disposal elucidated. (orig.) [de

  10. Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

    Science.gov (United States)

    Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

    2016-09-01

    A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

  11. Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

    Science.gov (United States)

    Hashemian, Mohammad Amin

    Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

  12. Historicising the Hydrosocial Cycle

    Directory of Open Access Journals (Sweden)

    Jeremy J. Schmidt

    2014-02-01

    Full Text Available This paper examines the historical claims made in support of the hydrosocial cycle. In particular, it considers how arguments advancing the hydrosocial cycle make historical claims regarding modernist conceptions of what water is (i.e. H2O and its fit with society. The paper gives special emphasis to the society/nature dualism and to the notion of agency as key sites of contest in arguments regarding the hydrosocial cycle. It finds that, while several versions of the hydrosocial cycle seek to advance a political ecology more sensitive to non-human actions, these same accounts often do not address the robust account of non-human agency in the historical record. Evidence is presented regarding water’s agency amongst late 19th and early 20th century architects of key water management norms in the United States. This evidence troubles accounts of the hydrosocial cycle that critique the US experience and suggests new directions for rethinking the role of historical and institutional norms in water policy.

  13. Hypoxia-inducible factor-1α plays roles in Epstein-Barr virus's natural life cycle and tumorigenesis by inducing lytic infection through direct binding to the immediate-early BZLF1 gene promoter.

    Directory of Open Access Journals (Sweden)

    Richard J Kraus

    2017-06-01

    Full Text Available When confronted with poor oxygenation, cells adapt by activating survival signaling pathways, including the oxygen-sensitive transcriptional regulators called hypoxia-inducible factor alphas (HIF-αs. We report here that HIF-1α also regulates the life cycle of Epstein-Barr virus (EBV. Incubation of EBV-positive gastric carcinoma AGS-Akata and SNU-719 and Burkitt lymphoma Sal and KemIII cell lines with a prolyl hydroxylase inhibitor, L-mimosine or deferoxamine, or the NEDDylation inhibitor MLN4924 promoted rapid and sustained accumulation of both HIF-1α and lytic EBV antigens. ShRNA knockdown of HIF-1α significantly reduced deferoxamine-mediated lytic reactivation. HIF-1α directly bound the promoter of the EBV primary latent-lytic switch BZLF1 gene, Zp, activating transcription via a consensus hypoxia-response element (HRE located at nt -83 through -76 relative to the transcription initiation site. HIF-1α did not activate transcription from the other EBV immediate-early gene, BRLF1. Importantly, expression of HIF-1α induced EBV lytic-gene expression in cells harboring wild-type EBV, but not in cells infected with variants containing base-pair substitution mutations within this HRE. Human oral keratinocyte (NOK and gingival epithelial (hGET cells induced to differentiate by incubation with either methyl cellulose or growth in organotypic culture accumulated both HIF-1α and Blimp-1α, another cellular factor implicated in lytic reactivation. HIF-1α activity also accumulated along with Blimp-1α during B-cell differentiation into plasma cells. Furthermore, most BZLF1-expressing cells observed in lymphomas induced by EBV in NSG mice with a humanized immune system were located distal to blood vessels in hypoxic regions of the tumors. Thus, we conclude that HIF-1α plays central roles in both EBV's natural life cycle and EBV-associated tumorigenesis. We propose that drugs that induce HIF-1α protein accumulation are good candidates for

  14. Self-catalytic stabilized Ag-Cu nanoparticles with tailored SERS response for plasmonic photocatalysis

    Science.gov (United States)

    He, Lili; Liu, Changqing; Tang, Jia; Zhou, Youchen; Yang, Hui; Liu, Ruiyu; Hu, Jiugang

    2018-03-01

    In-situ SERS monitoring of direct plasmon-driven photocatalysis was achieved using relatively earth-abundant Cu NPs following their decoration with tiny amounts of silver, which promoted excellent SERS and high catalytic activity. The SERS and catalytic performance of the Ag-Cu NPs can be tuned by changing their composition. In particular, it was found that the surface oxidation state of copper could be switched to its metallic state via self-plasmon catalysis under laser irradiation, highlighting the potential of air-unstable copper NPs as stable plasmonic catalysts. These dual functional Ag-Cu NPs were used for SERS real-time monitoring of plasmon-driven photocatalysis reactions involving the degradation of Rhodamine 6G and the dimerization of 4-nitrothiophenol. The corresponding catalytic reaction mechanisms were discussed.

  15. Reactivating Catalytic Surface: Insights into the Role of Hot Holes in Plasmonic Catalysis.

    Science.gov (United States)

    Peng, Tianhuan; Miao, Junjian; Gao, Zhaoshuai; Zhang, Linjuan; Gao, Yi; Fan, Chunhai; Li, Di

    2018-03-01

    Surface plasmon resonance of coinage metal nanoparticles is extensively exploited to promote catalytic reactions via harvesting solar energy. Previous efforts on elucidating the mechanisms of enhanced catalysis are devoted to hot electron-induced photothermal conversion and direct charge transfer to the adsorbed reactants. However, little attention is paid to roles of hot holes that are generated concomitantly with hot electrons. In this work, 13 nm spherical Au nanoparticles with small absorption cross-section are employed to catalyze a well-studied glucose oxidation reaction. Density functional theory calculation and X-ray absorption spectrum analysis reveal that hot holes energetically favor transferring catalytic intermediates to product molecules and then desorbing from the surface of plasmonic catalysts, resulting in the recovery of their catalytic activities. The studies shed new light on the use of the synergy of hot holes and hot electrons for plasmon-promoted catalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Effect of High-Pressure Treatment on Catalytic and Physicochemical Properties of Pepsin.

    Science.gov (United States)

    Wang, Jianan; Bai, Tenghui; Ma, Yaping; Ma, Hanjun

    2017-10-11

    For a long time, high-pressure treatment has been used to destroy the compact structures of natural proteins in order to promote subsequent enzymatic hydrolysis. However, there are few reports evaluating the feasibility of directly improving the catalytic capability of proteases by using high-pressure treatments. In this study, the effects of high-pressure treatment on the catalytic capacity and structure of pepsin were investigated, and the relationship between its catalytic properties and changes in its physicochemical properties was explored. It was found that high-pressure treatment could lead to changes of the sulfhydryl group/disulfide bond content, hydrophobicity, hydrodynamic radius, intrinsic viscosity, and subunit composition of pepsin, and the conformational change of pepsin resulted in improvement to its enzymatic activity and hydrolysis efficiency, which had an obvious relationship with the high-pressure treatment conditions.

  17. Characterization of the catalytic center of the Ebola virus L polymerase.

    Science.gov (United States)

    Schmidt, Marie Luisa; Hoenen, Thomas

    2017-10-01

    Ebola virus (EBOV) causes a severe hemorrhagic fever in humans and non-human primates. While no licensed therapeutics are available, recently there has been tremendous progress in developing antivirals. Targeting the ribonucleoprotein complex (RNP) proteins, which facilitate genome replication and transcription, and particularly the polymerase L, is a promising antiviral approach since these processes are essential for the virus life cycle. However, until now little is known about L in terms of its structure and function, and in particular the catalytic center of the RNA-dependent RNA polymerase (RdRp) of L, which is one of the most promising molecular targets, has never been experimentally characterized. Using multiple sequence alignments with other negative sense single-stranded RNA viruses we identified the putative catalytic center of the EBOV RdRp. An L protein with mutations in this center was then generated and characterized using various life cycle modelling systems. These systems are based on minigenomes, i.e. miniature versions of the viral genome, in which the viral genes are exchanged against a reporter gene. When such minigenomes are coexpressed with RNP proteins in mammalian cells, the RNP proteins recognize them as authentic templates for replication and transcription, resulting in reporter activity reflecting these processes. Replication-competent minigenome systems indicated that our L catalytic domain mutant was impaired in genome replication and/or transcription, and by using replication-deficient minigenome systems, as well as a novel RT-qPCR-based genome replication assay, we showed that it indeed no longer supported either of these processes. However, it still showed similar expression to wild-type L, and retained its ability to be incorporated into inclusion bodies, which are the sites of EBOV genome replication. We have experimentally defined the catalytic center of the EBOV RdRp, and thus a promising antiviral target regulating an essential

  18. Characterization of the catalytic center of the Ebola virus L polymerase.

    Directory of Open Access Journals (Sweden)

    Marie Luisa Schmidt

    2017-10-01

    Full Text Available Ebola virus (EBOV causes a severe hemorrhagic fever in humans and non-human primates. While no licensed therapeutics are available, recently there has been tremendous progress in developing antivirals. Targeting the ribonucleoprotein complex (RNP proteins, which facilitate genome replication and transcription, and particularly the polymerase L, is a promising antiviral approach since these processes are essential for the virus life cycle. However, until now little is known about L in terms of its structure and function, and in particular the catalytic center of the RNA-dependent RNA polymerase (RdRp of L, which is one of the most promising molecular targets, has never been experimentally characterized.Using multiple sequence alignments with other negative sense single-stranded RNA viruses we identified the putative catalytic center of the EBOV RdRp. An L protein with mutations in this center was then generated and characterized using various life cycle modelling systems. These systems are based on minigenomes, i.e. miniature versions of the viral genome, in which the viral genes are exchanged against a reporter gene. When such minigenomes are coexpressed with RNP proteins in mammalian cells, the RNP proteins recognize them as authentic templates for replication and transcription, resulting in reporter activity reflecting these processes. Replication-competent minigenome systems indicated that our L catalytic domain mutant was impaired in genome replication and/or transcription, and by using replication-deficient minigenome systems, as well as a novel RT-qPCR-based genome replication assay, we showed that it indeed no longer supported either of these processes. However, it still showed similar expression to wild-type L, and retained its ability to be incorporated into inclusion bodies, which are the sites of EBOV genome replication.We have experimentally defined the catalytic center of the EBOV RdRp, and thus a promising antiviral target

  19. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.

    2006-01-01

    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  20. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

  1. Complementary structure sensitive and insensitive catalytic relationships

    NARCIS (Netherlands)

    Santen, van R.A.

    2009-01-01

    The burgeoning field of nanoscience has stimulated an intense interest in properties that depend on particle size. For transition metal particles, one important property that depends on size is catalytic reactivity, in which bonds are broken or formed on the surface of the particles. Decreased

  2. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen

    2007-01-01

    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...... understanding of the nature of the electrochemical promotion is also presented....

  3. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang

    2015-09-01

    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  4. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan

    2007-01-01

    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  5. CATALYTIC SPECTROPHOTOMETRIC DETERMINATION OF Mn(II ...

    African Journals Online (AJOL)

    Preferred Customer

    method is based on the catalytic effect of Mn(II) with the oxidation of Celestine blue .... water samples were filtered through a 0.45 μm pore size membrane filter to remove suspended .... slope of the calibration graph as the optimization criterion. ..... In presence of Phen as stability enhancement agent in indicator system. ( ) +.

  6. Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

    NARCIS (Netherlands)

    Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

  7. Catalytic oxidation of cyclohexane to cyclohexanone

    Indian Academy of Sciences (India)

    ... a precursor and characterized by chemical analysis using the ICP–AES method, XRD, TEM, FTIR and BET surface area determination. The oxidation reaction was carried out at 70°C under atmospheric pressure. The results showed the catalytic performance of Pt/Al2O3 as being very high in terms of turnover frequency.

  8. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank

    2014-01-01

    45 (2006) 5330-5342]. This behavior was investigated in the yeast enzyme by mutations in the conserved catalytic loop and 5-phosphoribosyl-1-diphosphate (PRPP) binding motif. Although the reaction is mechanistically sequential, the wild-type (WT) enzyme shows parallel lines in double reciprocal...

  9. Flame assisted synthesis of catalytic ceramic membranes

    DEFF Research Database (Denmark)

    Johansen, Johnny; Mosleh, Majid; Johannessen, Tue

    2004-01-01

    technology it is possible to make supported catalysts, composite metal oxides, catalytically active surfaces, and porous ceramic membranes. Membrane layers can be formed by using a porous substrate tube (or surface) as a nano-particle filter. The aerosol gas from the flame is led through a porous substrate...

  10. Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

    Science.gov (United States)

    Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

    2014-01-09

    Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

  11. Sintering of Catalytic Nanoparticles: Particle Migration or Ostwald Ripening?

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; DeLaRiva, Andrew T.; Challa, Sivakumar R.

    2013-01-01

    deactivation, is an important mechanism for the loss of catalyst activity. This is especially true for high temperature catalytic processes, such as steam reforming, automotive exhaust treatment, or catalytic combustion. With dwindling supplies of precious metals and increasing demand, fundamental...

  12. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Unknown

    1995; Lyubovsky and Pfefferle 1999; Sales et al 1999;. Hill et al 2000). ... For a catalytic system, whose activity ... catalytic systems containing Pd, supported on various acid- ..... Further studies are needed to optimize a balance between.

  13. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2013-01-01

    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size

  14. Catalytic site identification—a web server to identify catalytic site structural matches throughout PDB

    Science.gov (United States)

    Kirshner, Daniel A.; Nilmeier, Jerome P.; Lightstone, Felice C.

    2013-01-01

    The catalytic site identification web server provides the innovative capability to find structural matches to a user-specified catalytic site among all Protein Data Bank proteins rapidly (in less than a minute). The server also can examine a user-specified protein structure or model to identify structural matches to a library of catalytic sites. Finally, the server provides a database of pre-calculated matches between all Protein Data Bank proteins and the library of catalytic sites. The database has been used to derive a set of hypothesized novel enzymatic function annotations. In all cases, matches and putative binding sites (protein structure and surfaces) can be visualized interactively online. The website can be accessed at http://catsid.llnl.gov. PMID:23680785

  15. TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

    International Nuclear Information System (INIS)

    Piotrowski, Piotr; Pawłowska, Joanna; Sadło, Jarosław Grzegorz; Bilewicz, Renata; Kaim, Andrzej

    2017-01-01

    C 60 TEMPO 10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C 60 TEMPO 10 @Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O 2 /Fe 3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

  16. Catalytic oligomerization of terminal alkynes promoted by organo-f-complexes

    International Nuclear Information System (INIS)

    Straub, T.; Haskel, A.; Eisen, M.S.

    1995-01-01

    Organoactinides of the type Cp* 2 AcMe 2 (Cp*=C 5 Me 5 ; Ac=Th, U) are active catalyst precursors for the oligomerization of terminal alkynes HC triple-bond CR (R=alkyl, aryl, SiMe 3 ). The regioselectivity and the extent of oligomerization strongly depend on the alkyne substituent R, whereas the catalytic reactivity is similar for 1 and 2. In the presence of one of these organoactinides, for example, HCCSiMe 3 regioselectively oligomerizes to the head-to-tail dimer 3 (5%) and the trimer 4 (95%). 1 and 2 react with the terminal alkynes, releasing methane, to the corresponding bisacetylide complexes which are active species and in the catalytic reactions. The bisacetylide complex (η 5 -C 5 Me 5 ) 2 U(CCPh) 2 was identified by proton NMR spectroscopy. Subsequent insertion of alkyne molecules in the actinide-carbon σ-bonds leads to the formation of actinide-alkenyl complexes. The turnover limiting step is the release of the organic oligomer from the actinide-organyl complex. A species of the latter has been spectroscopically characterized in the trimerization reaction of HCCSiMe 3 . In this poster, the catalytic reactivity of the actinide alkyls 1 and 2 with various mono-substituted alkynes as well as the spectroscopic characterization of the key organometallic intermediate complexes in the catalytic cycle and a detailed mechanistic discussion are given

  17. Extended Impact of Pin1 Catalytic Loop Phosphorylation Revealed by S71E Phosphomimetic.

    Science.gov (United States)

    Mahoney, Brendan J; Zhang, Meiling; Zintsmaster, John S; Peng, Jeffrey W

    2018-03-02

    Pin1 is a two-domain human protein that catalyzes the cis-trans isomerization of phospho-Ser/Thr-Pro (pS/T-P) motifs in numerous cell-cycle regulatory proteins. These pS/T-P motifs bind to Pin1's peptidyl-prolyl isomerase (PPIase) domain in a catalytic pocket, between an extended catalytic loop and the PPIase domain core. Previous studies showed that post-translational phosphorylation of S71 in the catalytic loop decreases substrate binding affinity and isomerase activity. To define the origins for these effects, we investigated a phosphomimetic Pin1 mutant, S71E-Pin1, using solution NMR. We find that S71E perturbs not only its host loop but also the nearby PPIase core. The perturbations identify a local network of hydrogen bonds and salt bridges that is more extended than previously thought, and includes interactions between the catalytic loop and the α2/α3 turn in the PPIase core. Explicit-solvent molecular dynamics simulations and phylogenetic analysis suggest that these interactions act as conserved "latches" between the loop and PPIase core that enhance binding of phosphorylated substrates, as they are absent in PPIases lacking pS/T-P specificity. Our results suggest that S71 is a hub residue within an electrostatic network primed for phosphorylation, and may illustrate a common mechanism of phosphorylation-mediated allostery. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. High-Compression-Ratio; Atkinson-Cycle Engine Using Low-Pressure Direct Injection and Pneumatic-Electronic Valve Actuation Enabled by Ionization Current and Foward-Backward Mass Air Flow Sensor Feedback

    Energy Technology Data Exchange (ETDEWEB)

    Harold Schock; Farhad Jaberi; Ahmed Naguib; Guoming Zhu; David Hung

    2007-12-31

    This report describes the work completed over a two and one half year effort sponsored by the US Department of Energy. The goal was to demonstrate the technology needed to produce a highly efficient engine enabled by several technologies which were to be developed in the course of the work. The technologies included: (1) A low-pressure direct injection system; (2) A mass air flow sensor which would measure the net airflow into the engine on a per cycle basis; (3) A feedback control system enabled by measuring ionization current signals from the spark plug gap; and (4) An infinitely variable cam actuation system based on a pneumatic-hydraulic valve actuation These developments were supplemented by the use of advanced large eddy simulations as well as evaluations of fuel air mixing using the KIVA and WAVE models. The simulations were accompanied by experimental verification when possible. In this effort a solid base has been established for continued development of the advanced engine concepts originally proposed. Due to problems with the valve actuation system a complete demonstration of the engine concept originally proposed was not possible. Some of the highlights that were accomplished during this effort are: (1) A forward-backward mass air flow sensor has been developed and a patent application for the device has been submitted. We are optimistic that this technology will have a particular application in variable valve timing direct injection systems for IC engines. (2) The biggest effort on this project has involved the development of the pneumatic-hydraulic valve actuation system. This system was originally purchased from Cargine, a Swedish supplier and is in the development stage. To date we have not been able to use the actuators to control the exhaust valves, although the actuators have been successfully employed to control the intake valves. The reason for this is the additional complication associated with variable back pressure on the exhaust valves when

  19. Long-Range Electrostatics-Induced Two-Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site.

    Science.gov (United States)

    Gerlits, Oksana; Wymore, Troy; Das, Amit; Shen, Chen-Hsiang; Parks, Jerry M; Smith, Jeremy C; Weiss, Kevin L; Keen, David A; Blakeley, Matthew P; Louis, John M; Langan, Paul; Weber, Irene T; Kovalevsky, Andrey

    2016-04-11

    Neutron crystallography was used to directly locate two protons before and after a pH-induced two-proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV-1 protease. The two-proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low-pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Catalytic Reduction of NO and NOx Content in Tobacco Smoke

    Directory of Open Access Journals (Sweden)

    Cvetkovic N

    2014-12-01

    Full Text Available In order to reduce the nitric oxide (NO and nitrogen oxides (NO content in mainstream tobacco smoke, a new class of catalyst based on Cu-ZSM-5 zeolite has been synthesized. The effectiveness of the new catalyst (degree of reduction and specific catalytic ability was tested both by adding Cu-ZSM-5 zeolite directly to the tobacco blend and by addition to the filter. We have determined that adding the catalyst to the tobacco blend does not cause any changes in the physical, chemical or organoleptic properties of the cigarette blend. But, the addition reduces the yield of nitrogen oxides while having no influence on nicotine and “tar” content in the tobacco smoke of the modified blend. The catalyst addition increases the static burning rate (SBR. The changes in the quantity of NO and NOmay be explained by changes in burning conditions due to the increase of Oobtained from catalytic degradation of NO and NO, and adsorptive and diffusive properties of the catalyst. The changes in mainstream smoke analytes are also given on a puff-by-puff basis.

  1. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe

    2018-01-22

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  2. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  3. Towards Prebiotic Catalytic Amyloids Using High Throughput Screening.

    Directory of Open Access Journals (Sweden)

    Michael P Friedmann

    Full Text Available Enzymes are capable of directing complex stereospecific transformations and of accelerating reaction rates many orders of magnitude. As even the simplest known enzymes comprise thousands of atoms, the question arises as to how such exquisite catalysts evolved. A logical predecessor would be shorter peptides, but they lack the defined structure and size that are apparently necessary for enzyme functions. However, some very short peptides are able to assemble into amyloids, thereby forming a well-defined tertiary structure called the cross-β-sheet, which bestows unique properties upon the peptides. We have hypothesized that amyloids could have been the catalytically active precursor to modern enzymes. To test this hypothesis, we designed an amyloid peptide library that could be screened for catalytic activity. Our approach, amenable to high-throughput methodologies, allowed us to find several peptides and peptide mixtures that form amyloids with esterase activity. These results indicate that amyloids, with their stability in a wide range of conditions and their potential as catalysts with low sequence specificity, would indeed be fitting precursors to modern enzymes. Furthermore, our approach can be efficiently expanded upon in library size, screening conditions, and target activity to yield novel amyloid catalysts with potential applications in aqueous-organic mixtures, at high temperature and in other extreme conditions that could be advantageous for industrial applications.

  4. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe; Wheeler, Janet I; Marondedze, Claudius; Gehring, Christoph A; Irving, Helen R

    2018-01-01

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  5. On Acyclicity of Games with Cycles

    DEFF Research Database (Denmark)

    Andersson, Daniel; Gurvich, Vladimir; Hansen, Thomas Dueholm

    2009-01-01

    We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (digraphs) that may contain cycles. We obtain criteria of restricted improvement acyclicity (ri-acyclicity) in two cases: for n = 2 and for acyclic digraphs. We...

  6. Safe cycling!

    CERN Multimedia

    Anaïs Schaeffer

    2012-01-01

    The HSE Unit will be running a cycling safety campaign at the entrances to CERN's restaurants on 14, 15 and 16 May. Pop along to see if they can persuade you to get back in the saddle!   With summer on its way, you might feel like getting your bike out of winter storage. Well, the HSE Unit has come up with some original ideas to remind you of some of the most basic safety rules. This year, the prevention campaign will be focussing on three themes: "Cyclists and their equipment", "The bicycle on the road", and "Other road users". This is an opportunity to think about the condition of your bike as well as how you ride it. From 14 to 16 May, representatives of the Swiss Office of Accident Prevention and the Touring Club Suisse will join members of the HSE Unit at the entrances to CERN's restaurants to give you advice on safe cycling (see box). They will also be organising three activity stands where you can test your knowle...

  7. Cycle 22

    International Nuclear Information System (INIS)

    Kappernman, J.G.; Albertson, V.D.

    1991-01-01

    This paper reports that for many electric utility systems, Solar Cycle 22 has been the first introduction to the phenomena of Geomagnetic Disturbances and the disrupting and damaging effects that they can have upon modern power systems. For all intents and purposes, Power Industry awareness of Cycle 22 started with a bang during the Great Geomagnetic Storm of March 13, 1989. This storm caused a blackout to the entire Province of Quebec, permanently damaged a large nuclear plant GSU transformer in New Jersey, and created enough havoc across the entire North American power grid to create the plausible threat of a massive power system blackout. The flurry of activity and investigation that followed has led many engineers to realize that their power systems are indeed vulnerable to this phenomena and if anything are becoming ever more vulnerable as the system grows to meet future requirements. As a result some organizations such as Hydro Quebec, PSE and G, and the PJM Pool now implement strategic measures as a remedial response to detection of geomagnetic storm conditions. Many more companies pay particularly close attention to storm forecasts and alerts, and the industry in general has accelerated research and monitoring activities through their own means of in concert with the Electric Power Research Institute (EPRI)

  8. The Geologic Nitrogen Cycle

    Science.gov (United States)

    Johnson, B. W.; Goldblatt, C.

    2013-12-01

    N2 is the dominant gas in Earth's atmosphere, and has been so through the majority of the planet's history. Originally thought to only be cycled in significant amounts through the biosphere, it is becoming increasingly clear that a large degree of geologic cycling can occur as well. N is present in crustal rocks at 10s to 100s of ppm and in the mantle at 1s to perhaps 10s of ppm. In light of new data, we present an Earth-system perspective of the modern N cycle, an updated N budget for the silicate Earth, and venture to explain the evolution of the N cycle over time. In an fashion similar to C, N has a fast, biologically mediated cycle and a slower cycle driven by plate tectonics. Bacteria fix N2 from the atmosphere into bioavailable forms. N is then cycled through the food chain, either by direct consumption of N-fixing bacteria, as NH4+ (the primary waste form), or NO3- (the most common inorganic species in the modern ocean). Some organic material settles as sediment on the ocean floor. In anoxic sediments, NH4+ dominates; due to similar ionic radii, it can readily substitute for K+ in mineral lattices, both in sedimentary rocks and in oceanic lithosphere. Once it enters a subduction zone, N may either be volatilized and returned to the atmosphere at arc volcanoes as N2 or N2O, sequestered into intrusive igneous rocks (as NH4+?), or subducted deep into the mantle, likely as NH4+. Mounting evidence indicates that a significant amount of N may be sequestered into the solid Earth, where it may remain for long periods (100s m.y.) before being returned to the atmosphere/biosphere by volcanism or weathering. The magnitude fluxes into the solid Earth and size of geologic N reservoirs are poorly constrained. The size of the N reservoirs contained in the solid Earth directly affects the evolution of Earth's atmosphere. It is possible that N now sequestered in the solid Earth was once in the atmosphere, which would have resulted in a higher atmospheric pressure, and

  9. Performance simulations of catalytic converters during the Federal Test Procedure

    Energy Technology Data Exchange (ETDEWEB)

    Shen, H.; Shamim, T.; Sengupta, S.; Son, S.; Adamczyk, A.A.

    1999-07-01

    A numerical study is carried out to predict the tailpipe emissions and emission conversion efficiencies of unburned hydrocarbon, nitrogen oxide and carbon monoxide flowing through a catalytic converter during the Federal Test Procedure (FTP). The model considers the effect of heat transfer in the catalytic converter, coupled with catalyst chemical kinetics, including an oxygen storage mechanism. The resulting governing equations based on the conservation of mass and energy are solved by a tridiagonal matrix algorithm (TDMA) with a successive line under relaxation method. The numerical scheme for this non-linear problem is found to have good convergence efficiency. The simulation for the complete FTP cycle is accomplished in less than fifteen minutes on a desktop personal computer. A 13-step reaction mechanism plus a nine-step O{sub 2} storage mechanism is used to simulate the chemical kinetics. The energy equations include the heat loss due to conduction and convection plus the energy liberated by chemical reactions. The effect of radiation is assumed to be negligible and is not considered. The results of the numerical model for both the instantaneous and accumulated emissions are found to be in good agreement with experimental measurements. The conversion efficiencies of HC, CO and NO as predicted by the model are found to be within 5% of those dynamic measurements, and calculated results of accumulated HC, CO and NO{sub x} are in fair agreement with experimental measurements. The transient measurements are also used to check the robustness of the numerical model. The model is found to be robust and hence can simulate various operating conditions of engine output to the converter.

  10. A Hybrid Catalytic Route to Fuels from Biomass Syngas

    Energy Technology Data Exchange (ETDEWEB)

    Harmon, Laurel [LanzaTech, Inc., Skokie, IL (United States); Hallen, Richard [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lilga, Michael [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heijstra, Bjorn [LanzaTech, Inc., Skokie, IL (United States); Palou-Rivera, Ignasi [LanzaTech, Inc., Skokie, IL (United States); Handler, Robert [Michigan Technological Univ., Houghton, MI (United States)

    2017-12-31

    feed, syngas composition, and impurities. Ethanol feedstocks from all three types of biomass were demonstrated to be comparable to grain derived ethanol and suitable for the LT-PNNL ATJ process. The LT-PNNL ATJ catalytic upgrading process was demonstrated at lab scale for over 2000 hours of continuous operation on a single catalyst load. LanzaTech scaled up the ATJ process, producing 4000 gallons of jet and 600 gallons of diesel for testing and a future proving flight. The LT-PNNL ATJ process, at lab and pilot scale, using commercial grain-based ethanol and steel mill waste gas-based ethanol (“Lanzanol”), produces high-quality fuel-range distillates containing primarily normal paraffins and isoparaffins. The LT-PNNL ATJ fuel has equivalent properties to previously-approved SPKs such as F-T, HEFA, and ATJ from isobutanol, and conforms with critical properties needed to blend with conventional jet fuel. The project showed that the 2,3-BDO fermentation co-product can be separated economically utilizing Simulated Moving Bed (SMB) technology. 2,3-BDO can be catalytically converted to 1,3-butadiene (BD) in a two-step process with at least 70% yield, producing a chemical intermediate suitable for downstream applications. Technoeconomic and life cycle analyses of the biomass to jet process with and without 2,3-BDO production showed that capital costs are sensitive to the proportion of the 2,3-BDO co-product and biomass feedstock. The co-product 2,3-BDO, converted through to BD, significantly reduces the cash cost of production of the hydrocarbon fuels. Life cycle GHG emissions of ATJ SPK produced from biomass using a steam gasification system are projected to be significantly lower than those of conventional jet fuel. The project demonstrated that a high quality ATJ SPK, can be produced from biomass via a hybrid gas fermentation/catalytic route. Validation of the LT-PNNL ATJ process using a variety of ethanol feedstocks demonstrated the viability of a future model of

  11. Effect of inlet cone pipe angle in catalytic converter

    Science.gov (United States)

    Amira Zainal, Nurul; Farhain Azmi, Ezzatul; Arifin Samad, Mohd

    2018-03-01

    The catalytic converter shows significant consequence to improve the performance of the vehicle start from it launched into production. Nowadays, the geometric design of the catalytic converter has become critical to avoid the behavior of backpressure in the exhaust system. The backpressure essentially reduced the performance of vehicles and increased the fuel consumption gradually. Consequently, this study aims to design various models of catalytic converter and optimize the volume of fluid flow inside the catalytic converter by changing the inlet cone pipe angles. Three different geometry angles of the inlet cone pipe of the catalytic converter were assessed. The model is simulated in Solidworks software to determine the optimum geometric design of the catalytic converter. The result showed that by decreasing the divergence angle of inlet cone pipe will upsurge the performance of the catalytic converter.

  12. Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

    Science.gov (United States)

    Park, Sangki; Oh, Jungmo

    2018-05-01

    The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

  13. Functional tuning of the catalytic residue pKa in a de novo designed esterase.

    Science.gov (United States)

    Hiebler, Katharina; Lengyel, Zsófia; Castañeda, Carlos A; Makhlynets, Olga V

    2017-09-01

    AlleyCatE is a de novo designed esterase that can be allosterically regulated by calcium ions. This artificial enzyme has been shown to hydrolyze p-nitrophenyl acetate (pNPA) and 4-nitrophenyl-(2-phenyl)-propanoate (pNPP) with high catalytic efficiency. AlleyCatE was created by introducing a single-histidine residue (His 144 ) into a hydrophobic pocket of calmodulin. In this work, we explore the determinants of catalytic properties of AlleyCatE. We obtained the pK a value of the catalytic histidine using experimental measurements by NMR and pH rate profile and compared these values to those predicted from electrostatics pK a calculations (from both empirical and continuum electrostatics calculations). Surprisingly, the pK a value of the catalytic histidine inside the hydrophobic pocket of calmodulin is elevated as compared to the model compound pK a value of this residue in water. We determined that a short-range favorable interaction with Glu 127 contributes to the elevated pK a of His 144 . We have rationally modulated local electrostatic potential in AlleyCatE to decrease the pK a of its active nucleophile, His 144 , by 0.7 units. As a direct result of the decrease in the His 144 pK a value, catalytic efficiency of the enzyme increased by 45% at pH 6. This work shows that a series of simple NMR experiments that can be performed using low field spectrometers, combined with straightforward computational analysis, provide rapid and accurate guidance to rationally improve catalytic efficiency of histidine-promoted catalysis. Proteins 2017; 85:1656-1665. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  14. Functional cooperation between FACT and MCM is coordinated with cell cycle and differential complex formation

    Directory of Open Access Journals (Sweden)

    Lin Chih-Li

    2010-02-01

    Full Text Available Abstract Background Functional cooperation between FACT and the MCM helicase complex constitutes an integral step during DNA replication initiation. However, mode of regulation that underlies the proper functional interaction of FACT and MCM is poorly understood. Methods & Results Here we present evidence indicating that such interaction is coordinated with cell cycle progression and differential complex formation. We first demonstrate the existence of two distinct FACT-MCM subassemblies, FACT-MCM2/4/6/7 and FACT-MCM2/3/4/5. Both complexes possess DNA unwinding activity and are subject to cell cycle-dependent enzymatic regulation. Interestingly, analysis of functional attributes further suggests that they act at distinct, and possibly sequential, steps during origin establishment and replication initiation. Moreover, we show that the phosphorylation profile of the FACT-associated MCM4 undergoes a cell cycle-dependent change, which is directly correlated with the catalytic activity of the FACT-MCM helicase complexes. Finally, at the quaternary structure level, physical interaction between FACT and MCM complexes is generally dependent on persistent cell cycle and further stabilized upon S phase entry. Cessation of mitotic cycle destabilizes the complex formation and likely leads to compromised coordination and activities. Conclusions Together, our results correlate FACT-MCM functionally and temporally with S phase and DNA replication. They further demonstrate that enzymatic activities intrinsically important for DNA replication are tightly controlled at various levels, thereby ensuring proper progression of, as well as exit from, the cell cycle and ultimately euploid gene balance.

  15. Thermodynamic characteristics of a low concentration methane catalytic combustion gas turbine

    International Nuclear Information System (INIS)

    Yin, Juan; Su, Shi; Yu, Xin Xiang; Weng, Yiwu

    2010-01-01

    Low concentration methane, emitted from coal mines, landfill, animal waste, etc. into the atmosphere, is not only a greenhouse gas, but also a waste energy source if not utilised. Methane is 23 times more potent than CO 2 in terms of trapping heat in the atmosphere over a timeframe of 100 years. This paper studies a novel lean burn catalytic combustion gas turbine, which can be powered with about 1% methane (volume) in air. When this technology is successfully developed, it can be used not only to mitigate the methane for greenhouse gas reduction, but also to utilise such methane as a clean energy source. This paper presents our study results on the thermodynamic characteristics of this new lean burn catalytic combustion gas turbine system by conducting thermal performance analysis of the turbine cycle. The thermodynamic data including thermal efficiencies and exergy loss of main components of the turbine system are presented under different pressure ratios, turbine inlet temperatures and methane concentrations.

  16. Facile synthesis of palladium nanoparticle doped polyaniline nanowires in soft templates for catalytic applications

    Science.gov (United States)

    Kshirasagar, Krushna J.; Markad, Uddhav S.; Saha, Abhijit; Sharma, Kiran Kumar K.; Sharma, Geeta K.

    2017-02-01

    Palladium nanoparticles doped polyaniline (Pd-PANI) nanocomposite (NCs) is synthesized in surfactant based liquid crystalline mesophase by chemical oxidation followed by radiolysis. The confinement of the liquid crystalline mesophase facilitates polymerization of aniline monomers and their 1D growth into polyaniline (PANI) nanowires by using ammonium persulfate. The PANI nanowires have an average diameter of 30-40 nm. The in situ radiolytic reduction of palladium ions ensures uniform size distribution of the palladium (Pd) nanoparticles on the surface of the PANI nanowires. The synthesized Pd-PANI nanocomposites show wire like structures of PANI (diameter ~30-40 nm) on which Pd nanoparticles of the size 10 nm are decorated. The identical average diameter of the PANI nanowires before and post gamma irradiation suggest high stability of the PANI nanowires in liquid crystalline mesophase. Surface characterization of the NCs were carried out using BET and XPS. The catalytic activity of Pd-PANI NCs are investigated in the reduction of methylene blue (MB) and 4-nitro phenol (4-NP) by sodium borohydride (NaBH4). The kinetics of the Pd-PANI NCs catalysed reactions are analysed using the Langmuir-Hinshelwood model. The apparent rate constant (k app) for the MB and 4-NP reduction reactions is 29  ×  10-3 s-1 and 20  ×  10-3 s-1 respectively with an actual Pd catalyst loading of 2.665  ×  10-4 ppm. Further, the recyclability of the Pd-PANI NCs catalyst in both the reduction reactions shows the stability of the catalyst up to four reaction cycles tested in this investigation and the multifunctional nature of the catalyst. The study provides a new approach for the directional synthesis of conducting polymer-metal nanocomposites and their possible application as a nanocatalyst in environmental remediation.

  17. Nitrogen removal from wastewater by a catalytic oxidation method.

    Science.gov (United States)

    Huang, T L; Macinnes, J M; Cliffe, K R

    2001-06-01

    The ammonia-containing waste produced in industries is usually characterized by high concentration and high temperature, and is not treatable by biological methods directly. In this study, a hydrophobic Pt/SDB catalyst was first used in a trickle-bed reactor to remove ammonia from wastewater. In the reactor, both stripping and catalytic oxidation occur simultaneously. It was found that higher temperature and higher oxygen partial pressure enhanced the ammonia removal. A reaction pathway, which involves oxidizing ammonia to nitric oxide, which then further reacts with ammonia to produce nitrogen and water, was confirmed. Small amounts of by-products, nitrites and nitrates were also detected in the resultant reaction solution. These compounds came from the absorption of nitrogen oxides. Both the minimum NO2- selectivity and maximum ammonia removal were achieved when the resultant pH of treated water was near 7.5 for a feed of unbuffered ammonia solution.

  18. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    Natural gas conversion remains one of the essential technologies for current energy needs. This review focuses on the mechanistic aspects of the development of efficient and durable catalysts for two reactions, carbon dioxide reforming and the oxidative coupling of methane. These two reactions have tremendous technological significance for practical application in industry. An understanding of the fundamental aspects and reaction mechanisms of the catalytic reactions reviewed in this study would support the design of industrial catalysts. CO 2 reforming of methane utilizes CO 2, which is often stored in large quantities, to convert as a reactant. Strategies to eliminate carbon deposition, which is the major problem associated with this reaction, are discussed. The oxidative coupling of methane directly produces ethylene in one reactor through a slightly exothermic reaction, potentially minimizing the capital cost of the natural gas conversion process. The focus of discussion in this review will be on the attainable yield of C 2 products by rigorous kinetic analyses.

  19. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1990-01-01

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  20. Zeolitic catalytic conversion of alcohols to hydrocarbons

    Science.gov (United States)

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

    2018-04-10

    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  1. Method to produce catalytically active nanocomposite coatings

    Science.gov (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2016-02-09

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  2. Enantioselective catalytic fluorinative aza-semipinacol rearrangement.

    Science.gov (United States)

    Romanov-Michailidis, Fedor; Pupier, Marion; Besnard, Céline; Bürgi, Thomas; Alexakis, Alexandre

    2014-10-03

    An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.

  3. Zeolitic catalytic conversion of alochols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-03

    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100.degree. C. and up to 550.degree. C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  4. Materials for High-Temperature Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Ersson, Anders

    2003-04-01

    Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

  5. Catalytic extraction processing of contaminated scrap metal

    International Nuclear Information System (INIS)

    Griffin, T.P.; Johnston, J.E.; Payea, B.M.; Zeitoon, B.M.

    1995-01-01

    Molten Metal Technology was awarded a contract to demonstrate the applicability of the Catalytic Extraction Process, a proprietary process that could be applied to US DOE's inventory of low level mixed waste. This paper is a description of that technology, and included within this document are discussions of: (1) Program objectives, (2) Overall technology review, (3) Organic feed conversion to synthetic gas, (4) Metal, halogen, and transuranic recovery, (5) Demonstrations, (6) Design of the prototype facility, and (7) Results

  6. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

    2017-12-19

    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  7. HTGR fuel and fuel cycle technology

    International Nuclear Information System (INIS)

    Lotts, A.L.; Coobs, J.H.

    1976-08-01

    The status of fuel and fuel cycle technology for high-temperature gas-cooled reactors (HTGRs) is reviewed. The all-ceramic core of the HTGRs permits high temperatures compared with other reactors. Core outlet temperatures of 740 0 C are now available for the steam cycle. For advanced HTGRs such as are required for direct-cycle power generation and for high-temperature process heat, coolant temperatures as high as 1000 0 C may be expected. The paper discusses the variations of HTGR fuel designs that meet the performance requirements and the requirements of the isotopes to be used in the fuel cycle. Also discussed are the fuel cycle possibilities, which include the low-enrichment cycle, the Th- 233 U cycle, and plutonium utilization in either cycle. The status of fuel and fuel cycle development is summarized

  8. Carbon cycle

    Energy Technology Data Exchange (ETDEWEB)

    Jaeger, J; Halbritter, G; Neumann-Hauf, G

    1982-05-01

    This report contains a review of literature on the subjects of the carbon cycle, the increase of the atmospheric CO/sub 2/ concentration and the possible impacts of an increased CO/sub 2/ concentration on the climate. In addition to this survey, the report discusses the questions that are still open and the resulting research needs. During the last twenty years a continual increase of the atmospheric carbon dioxide concentration by about 1-2 ppm per years has been observed. In 1958 the concentration was 315 ppm and this increased to 336 ppm in 1978. A rough estimate shows that the increase of the atmospheric carbon dioxide concentration is about half of the amount of carbon dioxide added to the atmosphere by the combustion of fossil fuels. Two possible sinks for the CO/sub 2/ released into the atmosphere are known: the ocean and the biota. The role of the biota is, however, unclear, since it can act both as a sink and as a source. Most models of the carbon cycle are one-dimensional and cannot be used for accurate predictions. Calculations with climate models have shown that an increased atmospheric CO/sub 2/ concentration leads to a warming of the earth's surface and lower atmosphere. Calculations show that a doubling of the atmospheric CO/sub 2/-concentration would lead to a net heating of the lower atmosphere and earth's surface by a global average of about 4 W m/sup -2/. Greater uncertainties arise in estimating the change in surface temperature resulting from this change in heating rate. It is estimated that the global average annual surface temperature would change between 1.5 and 4.5 K. There are, however, latitudinal and seasonal variations of the impact of increased CO/sub 2/ concentration. Other meteorological variables (e.g. precipitation, wind speed etc.) would also be changed. It appears that the impacts of the other products of fossil fuel combustion are unlikely to counteract the impacts of CO/sub 2/ on the climate.

  9. Catalytic hydrogen recombination for nuclear containments

    International Nuclear Information System (INIS)

    Koroll, G.W.; Lau, D.W.P.; Dewit, W.A.; Graham, W.R.C.

    1994-01-01

    Catalytic recombiners appear to be a credible option for hydrogen mitigation in nuclear containments. The passive operation, versatility and ease of back fitting are appealing for existing stations and new designs. Recently, a generation of wet-proofed catalyst materials have been developed at AECL which are highly specific to H 2 -O 2 , are active at ambient temperatures and are being evaluated for containment applications. Two types of catalytic recombiners were evaluated for hydrogen removal in containments based on the AECL catalyst. The first is a catalytic combustor for application in existing air streams such as provided by fans or ventilation systems. The second is an autocatalytic recombiner which uses the enthalpy of reaction to produce natural convective flow over the catalyst elements. Intermediate-scale results obtained in 6 m 3 and 10 m 3 spherical and cylindrical vessels are given to demonstrate self-starting limits, operating limits, removal capacity, scaling parameters, flow resistance, mixing behaviour in the vicinity of an operating recombiner and sensitivity to poisoning, fouling and radiation. (author). 13 refs., 10 figs

  10. Electrochemical catalytic treatment of phenol wastewater

    International Nuclear Information System (INIS)

    Ma Hongzhu; Zhang Xinhai; Ma Qingliang; Wang Bo

    2009-01-01

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  11. Catalytic applications of bio-inspired nanomaterials

    Science.gov (United States)

    Pacardo, Dennis Kien Balaong

    The biomimetic synthesis of Pd nanoparticles was presented using the Pd4 peptide, TSNAVHPTLRHL, isolated from combinatorial phage display library. Using this approach, nearly monodisperse and spherical Pd nanoparticles were generated with an average diameter of 1.9 +/- 0.4 nm. The peptide-based nanocatalyst were employed in the Stille coupling reaction under energy-efficient and environmentally friendly reaction conditions of aqueous solvent, room temperature and very low catalyst loading. To this end, the Pd nanocatalyst generated high turnover frequency (TOF) value and quantitative yields using ≥ 0.005 mol% Pd as well as catalytic activities with different aryl halides containing electron-withdrawing and electron-donating groups. The Pd4-capped Pd nanoparticles followed the atom-leaching mechanism and were found to be selective with respect to substrate identity. On the other hand, the naturally-occurring R5 peptide (SSKKSGSYSGSKGSKRRIL) was employed in the synthesis of biotemplated Pd nanomaterials which showed morphological changes as a function of Pd:peptide ratio. TOF analysis for hydrogenation of olefinic alcohols showed similar catalytic activity regardless of nanomorphology. Determination of catalytic properties of these bio-inspired nanomaterials are important as they serve as model system for alternative green catalyst with applications in industrially important transformations.

  12. Catalytic pyrolysis of olive mill wastewater sludge

    Science.gov (United States)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  13. Antibody proteases: induction of catalytic response.

    Science.gov (United States)

    Gabibov, A G; Friboulet, A; Thomas, D; Demin, A V; Ponomarenko, N A; Vorobiev, I I; Pillet, D; Paon, M; Alexandrova, E S; Telegin, G B; Reshetnyak, A V; Grigorieva, O V; Gnuchev, N V; Malishkin, K A; Genkin, D D

    2002-10-01

    Most of the data accumulated throughout the years on investigation of catalytic antibodies indicate that their production increases on the background of autoimmune abnormalities. The different approaches to induction of catalytic response toward recombinant gp120 HIV-1 surface protein in mice with various autoimmune pathologies are described. The peptidylphosphonate conjugate containing structural part of gp120 molecule is used for reactive immunization of NZB/NZW F1, MRL, and SJL mice. The specific modification of heavy and light chains of mouse autoantibodies with Val-Ala-Glu-Glu-Glu-Val-PO(OPh)2 reactive peptide was demonstrated. Increased proteolytic activity of polyclonal antibodies in SJL mice encouraged us to investigate the production of antigen-specific catalytic antibodies on the background of induced experimental autoimmune encephalomyelitis (EAE). The immunization of autoimmune-prone mice with the engineered fusions containing the fragments of gp120 and encephalitogenic epitope of myelin basic protein (MBP(89-104)) was made. The proteolytic activity of polyclonal antibodies isolated from the sera of autoimmune mice immunized by the described antigen was shown. Specific immune response of SJL mice to these antigens was characterized. Polyclonal antibodies purified from sera of the immunized animals revealed proteolytic activity. The antiidiotypic approach to raise the specific proteolytic antibody as an "internal image" of protease is described. The "second order" monoclonal antibodies toward subtilisin Carlsberg revealed pronounced proteolytic activity.

  14. Electrochemical catalytic treatment of phenol wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Ma Hongzhu, E-mail: hzmachem@snnu.edu.cn [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Zhang Xinhai [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China); Ma Qingliang [Department of Applied Physics, College of Sciences, Taiyuan University of Technology, 030024 Taiyuan (China); Wang Bo [Institute of Energy Chemistry, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

    2009-06-15

    The slurry bed catalytic treatment of contaminated water appears to be a promising alternative for the oxidation of aqueous organic pollutants. In this paper, the electrochemical oxidation of phenol in synthetic wastewater catalyzed by ferric sulfate and potassium permanganate adsorbed onto active bentonite in slurry bed electrolytic reactor with graphite electrode has been investigated. In order to determine the optimum operating condition, the orthogonal experiments were devised and the results revealed that the system of ferric sulfate, potassium permanganate and active bentonite showed a high catalytic efficiency on the process of electrochemical oxidation phenol in initial pH 5. When the initial concentration of phenol was 0.52 g/L (the initial COD 1214 mg/L), up to 99% chemical oxygen demand (COD) removal was obtained in 40 min. According to the experimental results, a possible mechanism of catalytic degradation of phenol was proposed. Environmental estimation was also done and the results showed that the treated wastewater have little impact on plant growth and could totally be applied to irrigation.

  15. Your Menstrual Cycle

    Science.gov (United States)

    ... your menstrual cycle What happens during your menstrual cycle The menstrual cycle includes not just your period, but the rise ... that take place over the weeks in your cycle. Want to know what happens on each day ...

  16. Cell cycle-specific UNG2 phosphorylations regulate protein turnover, activity and association with RPA

    DEFF Research Database (Denmark)

    Hagen, Lars; Kavli, Bodil; Sousa, Mirta M L

    2008-01-01

    -catalytic domain that confer distinct functional properties to UNG2. These are apparently generated by cyclin-dependent kinases through stepwise phosphorylation of S23, T60 and S64 in the cell cycle. Phosphorylation of S23 in late G1/early S confers increased association with replication protein A (RPA......) and replicating chromatin and markedly increases the catalytic turnover of UNG2. Conversely, progressive phosphorylation of T60 and S64 throughout S phase mediates reduced binding to RPA and flag UNG2 for breakdown in G2 by forming a cyclin E/c-myc-like phosphodegron. The enhanced catalytic turnover of UNG2 p-S23...

  17. Preparation of silver nanoparticles/polydopamine functionalized polyacrylonitrile fiber paper and its catalytic activity for the reduction 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Shixiang, E-mail: shixianglu@bit.edu.cn [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Yu, Jianying; Cheng, Yuanyuan [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang, Qian; Barras, Alexandre [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Xu, Wenguo [School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China); Szunerits, Sabine [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France); Cornu, David [Institut Européen des Membranes, UMR 5635, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), CNRS, Université Montpellier 2, 276 rue de la Galéra, Montpellier 34000 (France); Boukherroub, Rabah, E-mail: rabah.boukherroub@iemn.univ-lille1.fr [Univ. Lille, CNRS, Centrale Lille, ISEN, Univ. Valenciennes, UMR 8520 – IEMN, Lille F-59000 (France)

    2017-07-31

    Graphical abstract: Illustration of the preparation of Ag nanoparticles coated paper and its catalytic application for 4-nitrophenol reduction into the corresponding 4-aminophenol. - Highlights: • Polyacrylonitrile paper was functionalized with polydopamine and Ag nanoparticles. • Polydopamine coating layer played both reductive and adhesive roles. • The composite material displayed good catalytic activity for 4-nitrophenol reduction. • The process was environmentally benign and facile. - Abstract: The study reports on the preparation of polyacrylonitrile fiber paper (PANFP) functionalized with polydopamine (PD) and silver nanoparticles (Ag NPs), named as Ag NPs/PD/PANFP. The composite material was obtained via a simple two-step chemical process. First, a thin polydopamine layer was coated onto the PANFP surface through immersion into an alkaline dopamine (pH 8.5) aqueous solution at room temperature. The reductive properties of polydopamine were further exploited for the deposition of Ag NPs. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy (SEM), X-ray diffraction pattern (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the nanocomposite was evaluated for the reduction of 4-nitrophenol using sodium borohydride (NaBH{sub 4}) at room temperature. The Ag NPs/PD/PANFP displayed good catalytic performance with a full reduction of 4-nitrophenol into the corresponding 4-aminophenol within 30 min. Moreover, the composite material exhibited a good stability up to 4 cycles without a significant loss of its catalytic activity.

  18. Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

    Science.gov (United States)

    Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

    2018-04-01

    In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

  19. Direct determination of protonation states and visualization of hydrogen bonding in a glycoside hydrolase with neutron crystallography

    Science.gov (United States)

    Wan, Qun; Parks, Jerry M.; Hanson, B. Leif; Fisher, Suzanne Zoe; Ostermann, Andreas; Schrader, Tobias E.; Graham, David E.; Coates, Leighton; Langan, Paul; Kovalevsky, Andrey

    2015-01-01

    Glycoside hydrolase (GH) enzymes apply acid/base chemistry to catalyze the decomposition of complex carbohydrates. These ubiquitous enzymes accept protons from solvent and donate them to substrates at close to neutral pH by modulating the pKa values of key side chains during catalysis. However, it is not known how the catalytic acid residue acquires a proton and transfers it efficiently to the substrate. To better understand GH chemistry, we used macromolecular neutron crystallography to directly determine protonation and ionization states of the active site residues of a family 11 GH at multiple pD (pD = pH + 0.4) values. The general acid glutamate (Glu) cycles between two conformations, upward and downward, but is protonated only in the downward orientation. We performed continuum electrostatics calculations to estimate the pKa values of the catalytic Glu residues in both the apo- and substrate-bound states of the enzyme. The calculated pKa of the Glu increases substantially when the side chain moves down. The energy barrier required to rotate the catalytic Glu residue back to the upward conformation, where it can protonate the glycosidic oxygen of the substrate, is 4.3 kcal/mol according to free energy simulations. These findings shed light on the initial stage of the glycoside hydrolysis reaction in which molecular motion enables the general acid catalyst to obtain a proton from the bulk solvent and deliver it to the glycosidic oxygen. PMID:26392527

  20. The development of catalytic nucleophilic additions of terminal alkynes in water.

    Science.gov (United States)

    Li, Chao-Jun

    2010-04-20

    One of the major research endeavors in synthetic chemistry over the past two decades is the exploration of synthetic methods that work under ambient atmosphere with benign solvents, that maximize atom utilization, and that directly transform natural resources, such as renewable biomass, from their native states into useful chemical products, thus avoiding the need for protecting groups. The nucleophilic addition of terminal alkynes to various unsaturated electrophiles is a classical (textbook) reaction in organic chemistry, allowing the formation of a C-C bond while simultaneously introducing the alkyne functionality. A prerequisite of this classical reaction is the stoichiometric generation of highly reactive metal acetylides. Over the past decade, our laboratory and others have been exploring an alternative, the catalytic and direct nucleophilic addition of terminal alkynes to unsaturated electrophiles in water. We found that various terminal alkynes can react efficiently with a wide range of such electrophiles in water (or organic solvent) in the presence of simple and readily available catalysts, such as copper, silver, gold, iron, palladium, and others. In this Account, we describe the development of these synthetic methods, focusing primarily on results from our laboratory. Our studies include the following: (i) catalytic reaction of terminal alkynes with acid chloride, (ii) catalytic addition of terminal alkynes to aldehydes and ketones, (iii) catalytic addition of alkynes to C=N bonds, and (iv) catalytic conjugate additions. Most importantly, these reactions can tolerate various functional groups and, in many cases, perform better in water than in organic solvents, clearly defying classical reactivities predicated on the relative acidities of water, alcohols, and terminal alkynes. We further discuss multicomponent and enantioselective reactions that were developed. These methods provide an alternative to the traditional requirement of separate steps in

  1. Turning goals into results: the power of catalytic mechanisms.

    Science.gov (United States)

    Collins, J

    1999-01-01

    Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

  2. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    International Nuclear Information System (INIS)

    Pozan, Gulin Selda

    2012-01-01

    Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  3. Cell Cycle Regulates Nuclear Stability of AID and Determines the Cellular Response to AID.

    Directory of Open Access Journals (Sweden)

    Quy Le

    2015-09-01

    Full Text Available AID (Activation Induced Deaminase deaminates cytosines in DNA to initiate immunoglobulin gene diversification and to reprogram CpG methylation in early development. AID is potentially highly mutagenic, and it causes genomic instability evident as translocations in B cell malignancies. Here we show that AID is cell cycle regulated. By high content screening microscopy, we demonstrate that AID undergoes nuclear degradation more slowly in G1 phase than in S or G2-M phase, and that mutations that affect regulatory phosphorylation or catalytic activity can alter AID stability and abundance. We directly test the role of cell cycle regulation by fusing AID to tags that destabilize nuclear protein outside of G1 or S-G2/M phases. We show that enforced nuclear localization of AID in G1 phase accelerates somatic hypermutation and class switch recombination, and is well-tolerated; while nuclear AID compromises viability in S-G2/M phase cells. We identify AID derivatives that accelerate somatic hypermutation with minimal impact on viability, which will be useful tools for engineering genes and proteins by iterative mutagenesis and selection. Our results further suggest that use of cell cycle tags to regulate nuclear stability may be generally applicable to studying DNA repair and to engineering the genome.

  4. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido

    2014-01-01

    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  5. Nanostructured, mesoporous Au/TiO2 model catalysts – structure, stability and catalytic properties

    Directory of Open Access Journals (Sweden)

    Matthias Roos

    2011-09-01

    Full Text Available Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100 substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES and X-ray photoelectron spectroscopy (XPS. The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit.

  6. International Business Cycle

    Directory of Open Access Journals (Sweden)

    Marek Lubiński

    2007-04-01

    Full Text Available Prime stylized facts of international business cycle theory refer to positive correlation in the cyclical components of important macroeconomic variables across countries. However a number of indicators of business cycle synchronization do not point to clear trends. It can be ascribed to the fact that different forces influence level of business cycle correlation. When investigating into the forces behind the commonness in aggregate fluctuations economic research seems to have pointed in two directions. One strand of the literature examines the idea of common exogenous shocks that affect economies simultaneously. In addition to that economic interdependencies such as trade in goods and services or capital account transactions may serve as the channels through which disturbances spill over across countries.The observed degree of output co movement reflects both the nature of the shocks that have occurred and the degree of economic interdependence. In the periods when common shocks prevail level of synchronization is usually higher than in times of transmission dominance.

  7. Advanced orient cycle, for strategic separation, transmutation and utilization of nuclides in the nuclear fuel cycle

    International Nuclear Information System (INIS)

    Ozawa, M.; Fujita, R.; Koyama, S.; Suzuki, T.; Fujii, Y.

    2007-01-01

    Electrolytic extraction (EE) method has been studied as a vital separation tool for new reprocessing process to realize transmutation and utilization of the specific fission products including LLFP * (e.g., Tc * , Ru, Rh, Pd * , Se * and Te * , etc) in the spent nuclear fuel. In an employed EE process, Pd 2 + cation itself would not only be easily (>99%) deposited from various nitric acid solutions, but enhance also the deposition of co-existing RuNO 3 + and ReO 4 - by acting as a catalyst (as Pd a datom). Such a catalytic electrolytic extraction (i.e., CEE) method was also applicable in the case of 9 9TcO 4 - deposition as well. Addition of Pd 2 + caused either to change the dendritic metal deposition form or to improve electrochemical property of deposits. The RMFP deposit, especially quaternary-, Pd-Ru-Rh-Re, deposits on the Pt electrode obtained by the CEE method were rather spherical in shape, seemed to be electrochemically agglomerated by nano particles. The deposits were stable and showed electrochemically nobler initial hydrogen evolution potential (φ H int.). Also in the given potential of -1.25 V (vs. Ag/AgCl), the quaternary-, Pd-Ru-Rh-Re, deposit Pt electrode suggested the highest cathodic current corresponding to the hydrogen generation reaction. Namely, those catalytic activities were ca. twice superior to that of the Pt electrode in alkaline solution. The sea water is a possible resource for hydrogen production in future. In the course of sea water electrolysis, disturbance due to Ca(OH) 2 and Mg(OH) 2 precipitation was inevitable, but the cathodic current of the quaternary deposit of RMFP was the highest, the same as to that of Pt electrode in the alkaline water. Therefore, RMFP has a potential to alternate with Pt catalyst. The electrochemical property of Re and 9 9Tc, as for alternative element to Re, are under investigation with a special interest of this direction of utilization. The renovative reprocessing flow sheet by tertiary pyridine resin

  8. Significance of the enzymatic properties of yeast S39A enolase to the catalytic mechanism.

    Science.gov (United States)

    Brewer, J M; Glover, C V; Holland, M J; Lebioda, L

    1998-04-02

    The S39A mutant of yeast enolase (isozyme 1), prepared by site-directed mutagenesis, has a relative Vmax of 0.01% and an activation constant for Mg2+ ca. 10-fold higher, compared with native enzyme. It is correctly folded. There is little effect of solvent viscosity on activity. We think that the loop Ser36-His43 fails to move to the 'closed' position upon catalytic Mg2+ binding, weakening several electrostatic interactions involved in the mechanism.

  9. Combined hydrothermal liquefaction and catalytic hydrothermal gasification system and process for conversion of biomass feedstocks

    Science.gov (United States)

    Elliott, Douglas C.; Neuenschwander, Gary G.; Hart, Todd R.

    2017-09-12

    A combined hydrothermal liquefaction (HTL) and catalytic hydrothermal gasification (CHG) system and process are described that convert various biomass-containing sources into separable bio-oils and aqueous effluents that contain residual organics. Bio-oils may be converted to useful bio-based fuels and other chemical feedstocks. Residual organics in HTL aqueous effluents may be gasified and converted into medium-BTU product gases and directly used for process heating or to provide energy.

  10. Catalytically stabilized combustion of lean methane-air-mixtures: a numerical model

    Energy Technology Data Exchange (ETDEWEB)

    Dogwiler, U; Benz, P; Mantharas, I [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The catalytically stabilized combustion of lean methane/air mixtures has been studied numerically under conditions closely resembling the ones prevailing in technical devices. A detailed numerical model has been developed for a laminar, stationary, 2-D channel flow with full heterogeneous and homogeneous reaction mechanisms. The computations provide direct information on the coupling between heterogeneous-homogeneous combustion and in particular on the means of homogeneous ignitions and stabilization. (author) 4 figs., 3 refs.

  11. Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

    Science.gov (United States)

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Catalytic cracking models developed for predictive control purposes

    Directory of Open Access Journals (Sweden)

    Dag Ljungqvist

    1993-04-01

    Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

  13. Protein structure based prediction of catalytic residues.

    Science.gov (United States)

    Fajardo, J Eduardo; Fiser, Andras

    2013-02-22

    Worldwide structural genomics projects continue to release new protein structures at an unprecedented pace, so far nearly 6000, but only about 60% of these proteins have any sort of functional annotation. We explored a range of features that can be used for the prediction of functional residues given a known three-dimensional structure. These features include various centrality measures of nodes in graphs of interacting residues: closeness, betweenness and page-rank centrality. We also analyzed the distance of functional amino acids to the general center of mass (GCM) of the structure, relative solvent accessibility (RSA), and the use of relative entropy as a measure of sequence conservation. From the selected features, neural networks were trained to identify catalytic residues. We found that using distance to the GCM together with amino acid type provide a good discriminant function, when combined independently with sequence conservation. Using an independent test set of 29 annotated protein structures, the method returned 411 of the initial 9262 residues as the most likely to be involved in function. The output 411 residues contain 70 of the annotated 111 catalytic residues. This represents an approximately 14-fold enrichment of catalytic residues on the entire input set (corresponding to a sensitivity of 63% and a precision of 17%), a performance competitive with that of other state-of-the-art methods. We found that several of the graph based measures utilize the same underlying feature of protein structures, which can be simply and more effectively captured with the distance to GCM definition. This also has the added the advantage of simplicity and easy implementation. Meanwhile sequence conservation remains by far the most influential feature in identifying functional residues. We also found that due the rapid changes in size and composition of sequence databases, conservation calculations must be recalibrated for specific reference databases.

  14. Catalytic effect of light illumination on bioleaching of chalcopyrite.

    Science.gov (United States)

    Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

    2015-04-01

    The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Tritium stripping by a catalytic exchange stripper

    International Nuclear Information System (INIS)

    Heung, L.K.; Gibson, G.W.; Ortman, M.S.

    1991-01-01

    A catalytic exchange process for stripping elemental tritium from gas streams has been demonstrated. The process uses a catalyzed isotopic exchange reaction between tritium in the gas phase and protium or deuterium in the solid phase on alumina. The reaction is catalyzed by platinum deposited on the alumina. The process has been tested with both tritium and deuterium. Decontamination factors (ration of inlet and outlet tritium concentrations) as high as 1000 have been achieved, depending on inlet concentration. The test results and some demonstrated applications are presented

  16. Plasma-catalytic reforming of liquid hydrocarbons

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  17. Methane combustion in catalytic premixed burners

    International Nuclear Information System (INIS)

    Cerri, I.; Saracco, G.; Specchia, V.

    1999-01-01

    Catalytic premixed burners for domestic boiler applications were developed with the aim of achieving a power modularity from 10 to 100% and pollutant emissions limited to NO x 2 , where the combustion took place entirely inside the burner heating it to incandescence and allowing a decrease in the flame temperature and NO x emissions. Such results were confirmed through further tests carried out in a commercial industrial-scale boiler equipped with the conical panels. All the results, by varying the excess air and the heat power employed, are presented and discussed [it

  18. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    International Nuclear Information System (INIS)

    Pourmortazavi, Seied Mahdi; Rahimi-Nasrabadi, Mehdi; Khalilian-Shalamzari, Morteza; Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh; Omrani, Ismail

    2012-01-01

    Graphical abstract: NiWO 4 nanoparticles were prepared via precipitation technique. Experimental parameters of procedure were optimized statistically. Highlights: ► NiWO 4 spherical nanoparticles were synthesized via direct precipitation method. ► Taguchi robust design was used for optimization of synthesis reaction parameters. ► Composition and structural properties of NiWO 4 nanoparticles were characterized. ► EDAX, XRD, SEM, FT-IR, UV–vis and photoluminescence techniques were employed. ► Catalytic activity of the product in a cyclo-addition reaction was investigated. - Abstract: Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO 4 nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO 4 particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO 4 were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV–vis spectroscopy, and photoluminescence. Finally, catalytic activity of the nanoparticles in a cycloaddition reaction was examined.

  19. Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pourmortazavi, Seied Mahdi, E-mail: pourmortazavi@yahoo.com [Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran (Iran, Islamic Republic of); Rahimi-Nasrabadi, Mehdi, E-mail: rahiminasrabadi@gmail.com [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Khalilian-Shalamzari, Morteza [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of); Zahedi, Mir Mahdi; Hajimirsadeghi, Seiedeh Somayyeh [Islamic Azad University, Varamin Pishva Branch, Varamin (Iran, Islamic Republic of); Omrani, Ismail [Department of Chemistry, Imam Hossein University, Tehran (Iran, Islamic Republic of)

    2012-12-15

    Graphical abstract: NiWO{sub 4} nanoparticles were prepared via precipitation technique. Experimental parameters of procedure were optimized statistically. Highlights: Black-Right-Pointing-Pointer NiWO{sub 4} spherical nanoparticles were synthesized via direct precipitation method. Black-Right-Pointing-Pointer Taguchi robust design was used for optimization of synthesis reaction parameters. Black-Right-Pointing-Pointer Composition and structural properties of NiWO{sub 4} nanoparticles were characterized. Black-Right-Pointing-Pointer EDAX, XRD, SEM, FT-IR, UV-vis and photoluminescence techniques were employed. Black-Right-Pointing-Pointer Catalytic activity of the product in a cyclo-addition reaction was investigated. - Abstract: Taguchi robust design was applied to optimize experimental parameters for controllable, simple and fast synthesis of nickel tungstate nanoparticles. NiWO{sub 4} nanoparticles were synthesized by precipitation reaction involving addition of nickel ion solution to the tungstate aqueous reagent and then formation of nickel tungstate nucleolus which are insoluble in aqueous media. Effects of various parameters such as nickel and tungstate concentrations, flow rate of reagent addition and reactor temperature on diameter of synthesized nickel tungstate nanoparticles were investigated experimentally by the aid of orthogonal array design. The results for analysis of variance (ANOVA) showed that particle size of nickel tungstate can be effectively tuned by controlling significant variables involving nickel and tungstate concentrations and flow rate; while, temperature of the reactor has a no considerable effect on the size of NiWO{sub 4} particles. The ANOVA results proposed the optimum conditions for synthesis of nickel tungstate nanoparticles via this technique. Also, under optimum condition nanoparticles of NiWO{sub 4} were prepared and their structure and chemical composition were characterized by means of EDAX, XRD, SEM, FT-IR spectroscopy, UV

  20. Comparative Life Cycle Assessment of Lignocellulosic Ethanol Production: Biochemical Versus Thermochemical Conversion

    Science.gov (United States)

    Mu, Dongyan; Seager, Thomas; Rao, P. Suresh; Zhao, Fu

    2010-10-01

    Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle

  1. Characterization of deactivated catalytic cracking catalyst and evaluation as absorbent material

    International Nuclear Information System (INIS)

    Valt, R.B.G.; Kaminari, N.M.S.; Cordeiro, B.; Ponte, M.J.J.S.; Ponte, H.A.

    2010-01-01

    One of the main uses of catalysts in the petroleum industry is in step catalytic cracking, which after use and regeneration cycles generates large quantities of waste material. In this research the deactivated FCC catalyst was characterized before and after the electrokinetic remediation process, in order to assess the change of its structure and possible adsorptive capacity. Analyses of X-Ray Fluorescence Spectroscopy, Scanning Electron Microscopy and BET surface area measurement were performed. The analysis showed no structural change due to the process employed and that electrokinetic remediation has recovered 42% of adsorption capacity of the material, by removing about 89% of heavy metals adhered initially in the catalyst surface. (author)

  2. Including lateral interactions into microkinetic models of catalytic reactions

    DEFF Research Database (Denmark)

    Hellman, Anders; Honkala, Johanna Karoliina

    2007-01-01

    In many catalytic reactions lateral interactions between adsorbates are believed to have a strong influence on the reaction rates. We apply a microkinetic model to explore the effect of lateral interactions and how to efficiently take them into account in a simple catalytic reaction. Three differ...... different approximations are investigated: site, mean-field, and quasichemical approximations. The obtained results are compared to accurate Monte Carlo numbers. In the end, we apply the approximations to a real catalytic reaction, namely, ammonia synthesis....

  3. A study on naphtha catalytic reforming reactor simulation and analysis.

    Science.gov (United States)

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-06-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  4. A study on naphtha catalytic reforming reactor simulation and analysis

    OpenAIRE

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei

    2005-01-01

    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation uni...

  5. Metal–Organic Frameworks Stabilize Mono(phosphine)–Metal Complexes for Broad-Scope Catalytic Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Lin, Zekai; Boures, Dean; An, Bing; Wang, Cheng; Lin, Wenbin (UC); (Xiamen)

    2016-08-10

    Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C–H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.

  6. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

    Science.gov (United States)

    Pozan, Gulin Selda

    2012-06-30

    The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Catalytic membrane in reduction of aqueous nitrates: operational principles and catalytic performance

    NARCIS (Netherlands)

    Ilinitch, O.M.; Cuperus, F.P.; Nosova, L.V.; Gribov, E.N.

    2000-01-01

    The catalytic membrane with palladium-copper active component supported over the macroporous ceramic membrane, and a series of γ-Al 2O 3 supported Pd-Cu catalysts were prepared and investigated. In reduction of nitrate ions by hydrogen in water at ambient temperature, pronounced internal diffusion

  8. Non-thermal plasmas for non-catalytic and catalytic VOC abatement

    International Nuclear Information System (INIS)

    Vandenbroucke, Arne M.; Morent, Rino; De Geyter, Nathalie; Leys, Christophe

    2011-01-01

    Highlights: → We review the current status of catalytic and non-catalytic VOC abatement based on a vast number of research papers. → The underlying mechanisms of plasma-catalysis for VOC abatement are discussed. → Critical process parameters that determine the influent are discussed and compared. - Abstract: This paper reviews recent achievements and the current status of non-thermal plasma (NTP) technology for the abatement of volatile organic compounds (VOCs). Many reactor configurations have been developed to generate a NTP at atmospheric pressure. Therefore in this review article, the principles of generating NTPs are outlined. Further on, this paper is divided in two equally important parts: plasma-alone and plasma-catalytic systems. Combination of NTP with heterogeneous catalysis has attracted increased attention in order to overcome the weaknesses of plasma-alone systems. An overview is given of the present understanding of the mechanisms involved in plasma-catalytic processes. In both parts (plasma-alone systems and plasma-catalysis), literature on the abatement of VOCs is reviewed in close detail. Special attention is given to the influence of critical process parameters on the removal process.

  9. Microwave Catalytic Oxidation of Hydrocarbons in Aqueous Solutions

    National Research Council Canada - National Science Library

    Cha, Chang

    2003-01-01

    .... A sufficient amount of experimental work has been completed evaluating the performance of the microwave catalytic oxidation process and determining the effect of different operating parameters...

  10. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-01-01

    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

  11. In-situ reduced silver nanoparticles on populus fiber and the catalytic application

    Energy Technology Data Exchange (ETDEWEB)

    Li, Miaomiao; Gong, Yumei, E-mail: ymgong@dlpu.edu.cn; Wang, Wenheng; Xu, Guangpeng; Liu, Yuanfa; Guo, Jing, E-mail: guojing8161@163.com

    2017-02-01

    Highlights: • A composite involved in in-situ chelating AgNPs on natural cellulose was prepared. • Polyamidoxime grafted from the cellulose adsorbed Ag+ which was reduced to AgNPs. • The composite exhibits excellent catalytic activity in reducing 4-nitrophenol. - Abstract: One kind of composites involved in silver nanoparticles (AgNPs) loading in-situ on natural populus fiber (PF) matrix was prepared by polyamidoxime (PAO) functionalized the cellulose fiber. In which PAO worked as trapping and stabilizing agents chelating silver ions and made it reduced in-situ to obtain AgNPs by borohydride at room temperature. The synthesized composites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Moreover, the composites showed significant catalytic activity 1.87 s{sup −1} g{sup −1} and repeated usability more than 7 cycles in reducing 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) detected by UV–vis spectrophotometer in aqueous solution due to the surface-enhanced immobility and large amount of AgNPs. The natural cellulose fiber provides a green platform to react and support other noble metals for wide catalytic reactions.

  12. The DNA topoisomerase II catalytic inhibitor merbarone is genotoxic and induces endoreduplication

    International Nuclear Information System (INIS)

    Pastor, Nuria; Domínguez, Inmaculada; Orta, Manuel Luís; Campanella, Claudia; Mateos, Santiago; Cortés, Felipe

    2012-01-01

    In the last years a number of reports have shown that the so-called topoisomerase II (topo II) catalytic inhibitors are able to induce DNA and chromosome damage, an unexpected result taking into account that they do not stabilize topo II-DNA cleavable complexes, a feature of topo II poisons such as etoposide and amsacrine. Merbarone inhibits the catalytic activity of topo II by blocking DNA cleavage by the enzyme. While it was first reported that merbarone does not induce genotoxic effects in mammalian cells, this has been challenged by reports showing that the topo II inhibitor induces efficiently chromosome and DNA damage, and the question as to a possible behavior as a topo II poison has been put forward. Given these contradictory results, and the as yet incomplete knowledge of the molecular mechanism of action of merbarone, in the present study we have tried to further characterize the mechanism of action of merbarone on cell proliferation, cell cycle, as well as chromosome and DNA damage in cultured CHO cells. Merbarone was cytotoxic as well as genotoxic, inhibited topo II catalytic activity, and induced endoreduplication. We have also shown that merbarone-induced DNA damage depends upon ongoing DNA synthesis. Supporting this, inhibition of DNA synthesis causes reduction of DNA damage and increased cell survival.

  13. Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

    2015-11-15

    Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

  14. Enhanced Hydrothermal Stability and Catalytic Performance of HKUST-1 by Incorporating Carboxyl-Functionalized Attapulgite.

    Science.gov (United States)

    Yuan, Bo; Yin, Xiao-Qian; Liu, Xiao-Qin; Li, Xing-Yang; Sun, Lin-Bing

    2016-06-29

    Much attention has been paid to metal-organic frameworks (MOFs) due to their large surface areas, tunable functionality, and diverse structure. Nevertheless, most reported MOFs show poor hydrothermal stability, which seriously hinders their applications. Here a strategy is adopted to tailor the properties of MOFs by means of incorporating carboxyl-functionalized natural clay attapulgite (ATP) into HKUST-1, a well-known MOF. A new type of hybrid material was thus fabricated from the hybridization of HKUST-1 and ATP. Our results indicated that the hydrothermal stability of the MOFs as well as the catalytic performance was apparently improved. The frameworks of HKUST-1 were severely destroyed after hydrothermal treatment (hot water vapor, 60 °C), while that of the hybrid materials was maintained. For the hybrid materials containing 8.4 wt % of ATP, the surface area reached 1302 m(2)·g(-1) and was even higher than that of pristine HKUST-1 (1245 m(2)·g(-1)). In the ring-opening of styrene oxide, the conversion reached 98.9% at only 20 min under catalysis from the hybrid material, which was obviously higher than that over pristine HKUST-1 (80.9%). Moreover, the hybrid materials showed excellent reusability and the catalytic activity was recoverable without loss after six cycles. Our materials provide promising candidates for heterogeneous catalysis owing to the good catalytic activity and reusability.

  15. Efficient Catalytic Conversion of Ethanol to 1-Butanol via the Guerbet Reaction over Copper- and Nickel-Doped Porous

    NARCIS (Netherlands)

    Sun, Zhuohua; Vasconcelos, Anais Couto; Bottari, Giovanni; Stuart, Marc C. A.; Bonura, Giuseppe; Cannilla, Catia; Frusteri, Francesco; Barta, Katalin

    The direct conversion of ethanol to higher value 1-butanol is a catalytic transformation of great interest in light of the expected wide availability of bioethanol originating from the fermentation of renewable resources. In this contribution we describe several novel compositions of porous metal

  16. Computational and Physical Analysis of Catalytic Compounds

    Science.gov (United States)

    Wu, Richard; Sohn, Jung Jae; Kyung, Richard

    2015-03-01

    Nanoparticles exhibit unique physical and chemical properties depending on their geometrical properties. For this reason, synthesis of nanoparticles with controlled shape and size is important to use their unique properties. Catalyst supports are usually made of high-surface-area porous oxides or carbon nanomaterials. These support materials stabilize metal catalysts against sintering at high reaction temperatures. Many studies have demonstrated large enhancements of catalytic behavior due to the role of the oxide-metal interface. In this paper, the catalyzing ability of supported nano metal oxides, such as silicon oxide and titanium oxide compounds as catalysts have been analyzed using computational chemistry method. Computational programs such as Gamess and Chemcraft has been used in an effort to compute the efficiencies of catalytic compounds, and bonding energy changes during the optimization convergence. The result illustrates how the metal oxides stabilize and the steps that it takes. The graph of the energy computation step(N) versus energy(kcal/mol) curve shows that the energy of the titania converges faster at the 7th iteration calculation, whereas the silica converges at the 9th iteration calculation.

  17. New separation technique. Catalytically functionated separation membrane

    Energy Technology Data Exchange (ETDEWEB)

    Urgami, Tadashi [Kansai Univ., Osaka (Japan)

    1989-02-01

    This report introduces research examples, showing the fundamental principle of the membrane by separating the catalytically functionated separation membrane into enzyme fixing separation membrane, polymerized metal complex separation membrane and polymer catalyst separation membrane. This membrane can achieve both functions of separation and catalytic reaction simultaneously and has sufficient possibility to combine powerful functions. Enzyme fixing separation membrane is prepared by carrier combination method, bridging method or covering method and the enzyme fixing method with polymerized complex in which enzyme is controlled to prevent the activity lowering as much as possible and enzyme is fixed from an aqueous solution into polymer membrane. This membrane is applied to the continuous manufacturing of invert sugar from cane sugar and adsorption and removing of harmful substances from blood by utilizing both micro-capsuled urease and active carbon. Alginic acid-copper (II) complex membrane is used for the polymerized metal complex membrane and polystyrene sulfonate membrane is used for the polymer catalyst separation membrane. 28 refs., 4 figs., 1 tabs.

  18. Study of catalytic phenomena in radiation chemistry

    International Nuclear Information System (INIS)

    Dran, J.C.

    1965-01-01

    Two phenomena have been studied: the action of γ rays from radio-cobalt on the adsorption and catalytic properties of ZnO and NiO in. relationship with the heterogeneous oxidation of CO, and the homogeneous catalysis by OsO 4 of the oxidation of various aqueous phase solutes by the same radiation. The prior irradiation of ZnO and of NiO does not modify their catalytic activity but generally increases the adsorption energy of -the gases CO and O 2 . The influence of the radiations appears to be connected with the presence of traces of water on ZnO and of an excess of oxygen on NiO. Osmium tetroxide which is not degraded by irradiation in acid solution, accelerates the radiolytic oxidation of certain compounds (Te IV , Pt 11 , As 111 ) in the presence of oxygen, as a result of its sensitizing effect on the oxidation by H 2 O 2 . In the case of phosphites on the other hand, OsO 4 has a protecting action under certain conditions of acidity and may suppress entirely the chain reaction which characterizes the oxidation of this solute byγ rays. A general mechanism is proposed for these phenomena. The rate constant for the OsO 4 + HO 2 reaction is calculated to be 5.7 x 10 5 l.mol -1 . sec -1 . (author) [fr

  19. Catalytic hydroprocessing of heavy oil feedstocks

    International Nuclear Information System (INIS)

    Okunev, A G; Parkhomchuk, E V; Lysikov, A I; Parunin, P D; Semeikina, V S; Parmon, V N

    2015-01-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references

  20. Catalytic hydroprocessing of heavy oil feedstocks

    Science.gov (United States)

    Okunev, A. G.; Parkhomchuk, E. V.; Lysikov, A. I.; Parunin, P. D.; Semeikina, V. S.; Parmon, V. N.

    2015-09-01

    A grave problem of modern oil refining industry is continuous deterioration of the produced oil quality, on the one hand, and increase in the demand for motor fuels, on the other hand. This necessitates processing of heavy oil feedstock with high contents of sulfur, nitrogen and metals and the atmospheric residue. This feedstock is converted to light oil products via hydrogenation processes catalyzed by transition metal compounds, first of all, cobalt- or nickel-promoted molybdenum and tungsten compounds. The processing involves desulfurization, denitrogenation and demetallization reactions as well as reactions converting heavy hydrocarbons to lighter fuel components. The review discusses the mechanisms of reactions involved in the heavy feedstock hydroprocessing, the presumed structure and state of the catalytically active components and methods for the formation of supports with the desired texture. Practically used and prospective approaches to catalytic upgrading of heavy oil feedstock as well as examples of industrial processing of bitumen and vacuum residues in the presence of catalysts are briefly discussed. The bibliography includes 140 references.

  1. Catalytic reactor for low-Btu fuels

    Science.gov (United States)

    Smith, Lance; Etemad, Shahrokh; Karim, Hasan; Pfefferle, William C.

    2009-04-21

    An improved catalytic reactor includes a housing having a plate positioned therein defining a first zone and a second zone, and a plurality of conduits fabricated from a heat conducting material and adapted for conducting a fluid therethrough. The conduits are positioned within the housing such that the conduit exterior surfaces and the housing interior surface within the second zone define a first flow path while the conduit interior surfaces define a second flow path through the second zone and not in fluid communication with the first flow path. The conduit exits define a second flow path exit, the conduit exits and the first flow path exit being proximately located and interspersed. The conduits define at least one expanded section that contacts adjacent conduits thereby spacing the conduits within the second zone and forming first flow path exit flow orifices having an aggregate exit area greater than a defined percent of the housing exit plane area. Lastly, at least a portion of the first flow path defines a catalytically active surface.

  2. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents.

    Science.gov (United States)

    Lushchekina, Sofya V; Schopfer, Lawrence M; Grigorenko, Bella L; Nemukhin, Alexander V; Varfolomeev, Sergei D; Lockridge, Oksana; Masson, Patrick

    2018-01-01

    Organophosphorus agents (OPs) are irreversible inhibitors of acetylcholinesterase (AChE). OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants ( k cat / K m > 10 6 M -1 min -1 ) are required, so that low enzyme doses can be administered. Cholinesterases (ChE) are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase) activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that introducing

  3. Optimization of Cholinesterase-Based Catalytic Bioscavengers Against Organophosphorus Agents

    Directory of Open Access Journals (Sweden)

    Sofya V. Lushchekina

    2018-03-01

    Full Text Available Organophosphorus agents (OPs are irreversible inhibitors of acetylcholinesterase (AChE. OP poisoning causes major cholinergic syndrome. Current medical counter-measures mitigate the acute effects but have limited action against OP-induced brain damage. Bioscavengers are appealing alternative therapeutic approach because they neutralize OPs in bloodstream before they reach physiological targets. First generation bioscavengers are stoichiometric bioscavengers. However, stoichiometric neutralization requires administration of huge doses of enzyme. Second generation bioscavengers are catalytic bioscavengers capable of detoxifying OPs with a turnover. High bimolecular rate constants (kcat/Km > 106 M−1min−1 are required, so that low enzyme doses can be administered. Cholinesterases (ChE are attractive candidates because OPs are hemi-substrates. Moderate OP hydrolase (OPase activity has been observed for certain natural ChEs and for G117H-based human BChE mutants made by site-directed mutagenesis. However, before mutated ChEs can become operational catalytic bioscavengers their dephosphylation rate constant must be increased by several orders of magnitude. New strategies for converting ChEs into fast OPase are based either on combinational approaches or on computer redesign of enzyme. The keystone for rational conversion of ChEs into OPases is to understand the reaction mechanisms with OPs. In the present work we propose that efficient OP hydrolysis can be achieved by re-designing the configuration of enzyme active center residues and by creating specific routes for attack of water molecules and proton transfer. Four directions for nucleophilic attack of water on phosphorus atom were defined. Changes must lead to a novel enzyme, wherein OP hydrolysis wins over competing aging reactions. Kinetic, crystallographic, and computational data have been accumulated that describe mechanisms of reactions involving ChEs. From these studies, it appears that

  4. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Hjelm, Anna-Karin [CATATOR AB, Lund (Sweden)

    2003-06-01

    Several independent studies show that gas stoves to some degree contribute to the indoor emissions of NO{sub x} especially in situations were the ventilation flow is poor. The peak-NO{sub x} concentrations can reach several hundred ppb but the integral concentration seldom exceeds about 20 - 50 ppb, which corresponds to an indoor-outdoor ratio of about 1 - 2.5. Epidemiological studies indicate increasing problems with respiratory symptoms in sensitive people at concentrations as low as 15 ppb of NO{sub 2}. Consequently, the NO{sub x}-concentration in homes where gas stoves are used is high enough to cause health effects. However, in situations where the ventilation flow is high (utilisation of ventilation hoods) the NO{sub x}-emissions are not likely to cause any health problems. This study has been aimed at investigating the possibilities to reduce the NO{sub x} emissions from gas stoves by replacing the conventional flame combustion with catalytic combustion. The investigation is requested by Swedish Gas Center, and is a following-up work of an earlier conducted feasibility study presented in April-2002. The present investigation reports on the possibility to use cheap and simple retro-fit catalytic design suggestions for traditional gas stoves. Experiments have been conducted with both natural and town gas, and parameters such as emissions of NO{sub x}, CO and unburned fuel gas and thermal efficiency, etc, have been examined and are discussed. The results show that it is possible to reduce the NO{sub x} emissions up to 80% by a simple retro-fit installation, without decreasing the thermal efficiency of the cooking plate. The measured source strengths correspond to indoor NO{sub x} concentrations that are below or equal to the average outdoor concentration, implying that no additional detrimental health effects are probable. The drawback of the suggested installations is that the concentration of CO and in some cases also CH{sub 4} are increased in the flue gases

  5. On the study of catalytic membrane reactor for water detritiation: Modeling approach

    Energy Technology Data Exchange (ETDEWEB)

    Liger, Karine, E-mail: karine.liger@cea.fr [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Mascarade, Jérémy [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France); Joulia, Xavier; Meyer, Xuan-Mi [Université de Toulouse, INPT, UPS, Laboratoire de Génie Chimique, 4, Allée Emile Monso, Toulouse F-31030 (France); CNRS, Laboratoire de Génie Chimique, Toulouse F-31030 (France); Troulay, Michèle; Perrais, Christophe [CEA, DEN, DTN/SMTA/LIPC Cadarache, Saint Paul-lez-Durance F-13108 (France)

    2016-11-01

    Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q{sub 2} form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

  6. On the study of catalytic membrane reactor for water detritiation: Modeling approach

    International Nuclear Information System (INIS)

    Liger, Karine; Mascarade, Jérémy; Joulia, Xavier; Meyer, Xuan-Mi; Troulay, Michèle; Perrais, Christophe

    2016-01-01

    Highlights: • Experimental results for the conversion of tritiated water (using deuterium as a simulant of tritium) by means of a catalytic membrane reactor in view of tritium recovery. • Phenomenological 2D model to represent catalytic membrane reactor behavior including the determination of the compositions of gaseous effluents. • Good agreement between the simulation results and experimental measurements performed on the dedicated facility. • Explanation of the unexpected behavior of the catalytic membrane reactor by the modeling results and in particular the gas composition estimation. - Abstract: In the framework of tritium recovery from tritiated water, efficiency of packed bed membrane reactors have been successfully demonstrated. Thanks to protium isotope swamping, tritium bonded water can be recovered under the valuable Q_2 form (Q = H, D or T) by means of isotope exchange reactions occurring on catalyst surface. The use of permselective Pd-based membrane allows withdrawal of reactions products all along the reactor, and thus limits reverse reaction rate to the benefit of the direct one (shift effect). The reactions kinetics, which are still little known or unknown, are generally assumed to be largely greater than the permeation ones so that thermodynamic equilibriums of isotope exchange reactions are generally assumed. This paper proposes a new phenomenological 2D model to represent catalytic membrane reactor behavior with the determination of gas effluents compositions. A good agreement was obtained between the simulation results and experimental measurements performed on a dedicated facility. Furthermore, the gas composition estimation permits to interpret unexpected behavior of the catalytic membrane reactor. In the next future, further sensitivity analysis will be performed to determine the limits of the model and a kinetics study will be conducted to assess the thermodynamic equilibrium of reactions.

  7. Patterned self-assembled monolayers for nanoscale lithography and the control of catalytically produced electroosmosis

    Science.gov (United States)

    Subramanian, Shyamala

    This thesis explores two applications of self-assembled monolayers (SAMs) (a) for developing novel molecular assembly based nanolithography techniques and (b) for tailoring zeta-potential of surfaces towards achieving directional control of catalytically induced fluid flow. The first half of the thesis develops the process of molecular ruler lithography using sacrificial host structures. This is a novel hybrid nanolithography technique which combines chemical self-assembly with conventional fabrication methods for improving the resolution of existing lithography tools to sub-50 nm. Previous work related to molecular ruler lithography have shown the use of thiol-SAMs, placed one on top of the other like a molecular resist, for scaling down feature sizes. In this thesis various engineering solutions for improving the reproducibility, yield, nanoscale roughness and overall manufacturability of the process are introduced. This is achieved by introducing a sacrificial inert layer underneath the gold parent structure. This bilayer sacrificial host allows for preferential, easy and quick removal of the parent structures, isolates the parent metal from the underlying substrate and improves reproducibility of the lift-off process. Also it opens avenues for fabrication of high aspect ratio features. Also molecular layer vapor deposition method is developed for building the multilayer molecular resist via vapor phase to reduce contaminations and yield issues associated with solution phase deposition. The smallest isolated metal features produced using this process were 40 nm in width. The second half of the thesis describes application of thiol-SAMs to tailor surface properties of gold, specifically the surface charge or zeta potential. Previous work has demonstrated that the direction of movement of fluid in the vicinity of a catalytically active bimetallic junction placed in a solution of dilute hydrogen peroxide depends on the charge of the gold surface. SAMs with

  8. Catalytic Enantioselective Alkylation of β-Keto Esters with Xanthydrol in the Presence of Chiral Palladium Complex

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kyu Yeon; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2016-01-15

    Our research interest has been directed toward the development of synthetic methods for the enantioselective construction of stereogenic carbon centers. Recently, we explored the catalytic enantioselective functionalization of active methines in the presence of chiral palladium(II) complexes. In conclusion, we have accomplished the efficient catalytic enantioselective alkylation of β-keto esters 1 with xanthydrol 2 with high yields and excellent enantioselectivity (up to 98% ee). It should be noted that this alkyaltion reaction proceeds well using air- and moisture-stable chiral palladium com- plexes with low loading (1 mol%)

  9. Highly Oriented Growth of Catalytically Active Zeolite ZSM‐5 Films with a Broad Range of Si/Al Ratios

    OpenAIRE

    Fu, Donglong; Schmidt, Joel E.; Ristanović, Zoran; Chowdhury, Abhishek Dutta; Meirer, Florian; Weckhuysen, Bert M.

    2017-01-01

    Abstract Highly b‐oriented zeolite ZSM‐5 films are critical for applications in catalysis and separations and may serve as models to study diffusion and catalytic properties in single zeolite channels. However, the introduction of catalytically active Al3+ usually disrupts the orientation of zeolite films. Herein, using structure‐directing agents with hydroxy groups, we demonstrate a new method to prepare highly b‐oriented zeolite ZSM‐5 films with a broad range of Si/Al ratios (Si/Al=45 to ∞)...

  10. Bipolar mood cycles and lunar tidal cycles.

    Science.gov (United States)

    Wehr, T A

    2018-04-01

    In 17 patients with rapid cycling bipolar disorder, time-series analyses detected synchronies between mood cycles and three lunar cycles that modulate the amplitude of the moon's semi-diurnal gravimetric tides: the 14.8-day spring-neap cycle, the 13.7-day declination cycle and the 206-day cycle of perigee-syzygies ('supermoons'). The analyses also revealed shifts among 1:2, 1:3, 2:3 and other modes of coupling of mood cycles to the two bi-weekly lunar cycles. These shifts appear to be responses to the conflicting demands of the mood cycles' being entrained simultaneously to two different bi-weekly lunar cycles with slightly different periods. Measurements of circadian rhythms in body temperature suggest a biological mechanism through which transits of one of the moon's semi-diurnal gravimetric tides might have driven the patients' bipolar cycles, by periodically entraining the circadian pacemaker to its 24.84-h rhythm and altering the pacemaker's phase-relationship to sleep in a manner that is known to cause switches from depression to mania.

  11. Catalytic Properties of the Isolated Diaphorase Fragment of the NAD+-Reducing [NiFe]-Hydrogenase from Ralstonia eutropha

    Science.gov (United States)

    Lauterbach, Lars; Idris, Zulkifli; Vincent, Kylie A.; Lenz, Oliver

    2011-01-01

    The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha H16 catalyzes the H2-driven reduction of NAD+, as well as reverse electron transfer from NADH to H+, in the presence of O2. It comprises six subunits, HoxHYFUI2, and incorporates a [NiFe] H+/H2 cycling catalytic centre, two non-covalently bound flavin mononucleotide (FMN) groups and an iron-sulfur cluster relay for electron transfer. This study provides the first characterization of the diaphorase sub-complex made up of HoxF and HoxU. Sequence comparisons with the closely related peripheral subunits of Complex I in combination with UV/Vis spectroscopy and the quantification of the metal and FMN content revealed that HoxFU accommodates a [2Fe2S] cluster, FMN and a series of [4Fe4S] clusters. Protein film electrochemistry (PFE) experiments show clear electrocatalytic activity for both NAD+ reduction and NADH oxidation with minimal overpotential relative to the potential of the NAD+/NADH couple. Michaelis-Menten constants of 56 µM and 197 µM were determined for NADH and NAD+, respectively. Catalysis in both directions is product inhibited with K I values of around 0.2 mM. In PFE experiments, the electrocatalytic current was unaffected by O2, however in aerobic solution assays, a moderate superoxide production rate of 54 nmol per mg of protein was observed, meaning that the formation of reactive oxygen species (ROS) observed for the native SH can be attributed mainly to HoxFU. The results are discussed in terms of their implications for aerobic functioning of the SH and possible control mechanism for the direction of catalysis. PMID:22016788

  12. A QM/MM study of the catalytic mechanism of nicotinamidase.

    Science.gov (United States)

    Sheng, Xiang; Liu, Yongjun

    2014-02-28

    Nicotinamidase (Pnc1) is a member of Zn-dependent amidohydrolases that hydrolyzes nicotinamide (NAM) to nicotinic acid (NA), which is a key step in the salvage pathway of NAD(+) biosynthesis. In this paper, the catalytic mechanism of Pnc1 has been investigated by using a combined quantum-mechanical/molecular-mechanical (QM/MM) approach based on the recently obtained crystal structure of Pnc1. The reaction pathway, the detail of each elementary step, the energetics of the whole catalytic cycle, and the roles of key residues and Zn-binding site are illuminated. Our calculation results indicate that the catalytic water molecule comes from the bulk solvent, which is then deprotonated by residue D8. D8 functions as a proton transfer station between C167 and NAM, while the activated C167 serves as the nucleophile. The residue K122 only plays a role in stabilizing intermediates and transition states. The oxyanion hole formed by the amide backbone nitrogen atoms of A163 and C167 has the function to stabilize the hydroxyl anion of nicotinamide. The Zn-binding site rather than a single Zn(2+) ion acts as a Lewis acid to influence the reaction. Two elementary steps, the activation of C167 in the deamination process and the decomposition of catalytic water in the hydrolysis process, correspond to the large energy barriers of 25.7 and 28.1 kcal mol(-1), respectively, meaning that both of them contribute a lot to the overall reaction barrier. Our results may provide useful information for the design of novel and efficient Pnc1 inhibitors and related biocatalytic applications.

  13. Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

    DEFF Research Database (Denmark)

    Sanchez, R.S.; Zhuravlev, Fedor

    2007-01-01

    The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

  14. A novel microalgal system for energy production with nitrogen cycling

    Energy Technology Data Exchange (ETDEWEB)

    Minowa, T.; Sawayama, S. [National Institute for Resources and Environment, Tsukuba (Japan)

    1999-08-01

    A microalga, Chlorella vulgaris, could grow in the recovered solution from the low temperature catalytic gasification of itself, by which methane rich fuel gas was obtained. All nitrogen in the microalga was converted to ammonia during the gasification, and the recovered solution, in which ammonia was dissolved, could be used as nitrogen nutrient. The result of the energy evaluation indicated that the novel microalgal system for energy production with nitrogen cycling could be created. 9 refs., 3 tabs.

  15. The Contemporary Carbon Cycle

    Science.gov (United States)

    Houghton, R. A.

    2003-12-01

    C). Additions of greenhouse gases to the atmosphere from industrial activity, however, are increasing the concentrations of these gases, enhancing the greenhouse effect, and starting to warm the Earth.The rate and extent of the warming depend, in part, on the global carbon cycle. If the rate at which the oceans remove CO2 from the atmosphere were faster, e.g., concentrations of CO2 would have increased less over the last century. If the processes removing carbon from the atmosphere and storing it on land were to diminish, concentrations of CO2 would increase more rapidly than projected on the basis of recent history. The processes responsible for adding carbon to, and withdrawing it from, the atmosphere are not well enough understood to predict future levels of CO2 with great accuracy. These processes are a part of the global carbon cycle.Some of the processes that add carbon to the atmosphere or remove it, such as the combustion of fossil fuels and the establishment of tree plantations, are under direct human control. Others, such as the accumulation of carbon in the oceans or on land as a result of changes in global climate (i.e., feedbacks between the global carbon cycle and climate), are not under direct human control except through controlling rates of greenhouse gas emissions and, hence, climatic change. Because CO2 has been more important than all of the other greenhouse gases under human control, combined, and is expected to continue so in the future, understanding the global carbon cycle is a vital part of managing global climate.This chapter addresses, first, the reservoirs and natural flows of carbon on the earth. It then addresses the sources of carbon to the atmosphere from human uses of land and energy and the sinks of carbon on land and in the oceans that have kept the atmospheric accumulation of CO2 lower than it would otherwise have been. The chapter describes changes in the distribution of carbon among the atmosphere, oceans, and terrestrial ecosystems over

  16. Hydrogen Production From catalytic reforming of greenhouse gases ...

    African Journals Online (AJOL)

    ADOWIE PERE

    a fixed bed stainless steel reactor. The 20wt%. ... catalytic activity for hydrogen production with the highest yield and selectivity of 32.5% and 17.6% respectively. © JASEM ... CO2 reforming of methane is however not fully developed ..... Design and preparation of .... catalytic nickel membrane for gas to liquid (GTL) process.

  17. Catalytic synthesis of ammonia using vibrationally excited nitrogen molecules

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Henriksen, Niels Engholm; Billing, Gert D.

    1992-01-01

    The dissociation of nitrogen is the rate-limiting step in the catalytic synthesis of ammonia. Theoretical calculations have shown that the dissociative sticking probability of molecular nitrogen on catalytic active metal surfaces is enhanced by orders of magnitude when the molecules...

  18. synthesis, characterization, electrical and catalytic studies of some

    African Journals Online (AJOL)

    B. S. Chandravanshi

    catalytic activity of the VO(IV) and Mn(III) complexes have been tested in the epoxidation reaction of styrene ... Vanadyl sulfate pentahydrate, chromium chloride hexahydrate, anhydrous ferric ..... The catalytic oxidation of styrene gives the products styrene oxide, benzaldehyde, benzoic acid, ... bond via a radical mechanism.

  19. Bibliography on cycling of trace metals in freshwater ecosystems

    International Nuclear Information System (INIS)

    LaRiviere, M.G.; Scott, A.J.; Woodfield, W.G.; Cushing, C.E.

    1978-07-01

    This bibliography is a listing of pertinent literature directly addressing the cycling of trace metals in freshwater ecosystems. Data on cycling, including the influences of environmental mediators, are included. 151 references

  20. MWW-type titanosilicate synthesis, structural modification and catalytic applications to green oxidations

    CERN Document Server

    Wu, Peng; Xu, Le; Liu, Yueming; He, Mingyuan

    2013-01-01

    This book provides a comprehensive review of a new generation of selective oxidation titanosilicate catalysts with the MWW topology (Ti-MWW) based on the research achievements of the past 12 years. It gives an overview of the synthesis, structure modification and catalytic properties of Ti-MWW. Ti-MWW can readily be prepared by means of direct hydrothermal synthesis with crystallization-supporting agents, using dual-structure-directing agents and a dry-gel conversion technique. It also can be post-synthesized through unique reversible structure transformation and liquid-phase isomorphous subst

  1. Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

    Science.gov (United States)

    You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

    2010-05-01

    Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

  2. Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

    Science.gov (United States)

    Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

    2018-02-09

    Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Catalytic monolayer voltammetry and in situ scanning tunneling microscopy of copper nitrite reductase on cysteamine-modified Au(111) electrodes

    DEFF Research Database (Denmark)

    Zhang, Jingdong; Welinder, A.C.; Hansen, Allan Glargaard

    2003-01-01

    electrochemical scanning tunneling microscopy (in situ STM) directly in aqueous acetate buffer, pH 6.0 has been used. High-resolution in situ STM shows that cysteamine packs into ordered domains with strip features of a periodic distance of 11.7 +/- 0.3 Angstrom. No voltammetric signals of the nitrite substrate...... on this surface could be detected. A strong cathodic catalytic wave appears in the presence of nitrite. The catalytic current follows a Michaelis-Menten pattern with a Michaelis constant of K-m approximate to 44 muM, which is close to the value for AxCuNiR in homogeneous solution. The apparent catalytic rate...

  4. Interactions of a Pop5/Rpp1 heterodimer with the catalytic domain of RNase MRP.

    Science.gov (United States)

    Perederina, Anna; Khanova, Elena; Quan, Chao; Berezin, Igor; Esakova, Olga; Krasilnikov, Andrey S

    2011-10-01

    Ribonuclease (RNase) MRP is a multicomponent ribonucleoprotein complex closely related to RNase P. RNase MRP and eukaryotic RNase P share most of their protein components, as well as multiple features of their catalytic RNA moieties, but have distinct substrate specificities. While RNase P is practically universally found in all three domains of life, RNase MRP is essential in eukaryotes. The structural organizations of eukaryotic RNase P and RNase MRP are poorly understood. Here, we show that Pop5 and Rpp1, protein components found in both RNase P and RNase MRP, form a heterodimer that binds directly to the conserved area of the putative catalytic domain of RNase MRP RNA. The Pop5/Rpp1 binding site corresponds to the protein binding site in bacterial RNase P RNA. Structural and evolutionary roles of the Pop5/Rpp1 heterodimer in RNases P and MRP are discussed.

  5. Structure and catalytic properties of metal β-diketonate complexes with oxygen-containing compounds

    International Nuclear Information System (INIS)

    Nizel'skij, Yu.N.; Ishchenko, S.S.; Lipatova, T.Eh.

    1985-01-01

    The results of researches published in recent 15-20 years of complexes of metal β-diketonates (including Cr 3+ , VO 2+ , MoOΛ2 2+ , Co 3+ , Mn 3+ , Ni 2+ , Fe 3+ ) with oxygen-containing compounds (alcohols, glycols, phenols, hydroperoxides, aldehydes, esters, etc.) playing an important role in catalytic processes of oxidation, addition, polymerization and copolymerization are reviewed. Data on the nature of chemical bond of oxygen-containing reacting agents with metal β-diketonates, on structure of metal β-diketonate complexes with oxygen-containing reacting agents and thermodynamics of complexing as well as on activation of reacting agents in complexes and catalytic properties of metal β-diketonates are discussed. Stored materials make it possible to exercise directed control of metal β-diketonate activity

  6. Catalytic microtubular jet engines self-propelled by accumulated gas bubbles.

    Science.gov (United States)

    Solovev, Alexander A; Mei, Yongfeng; Bermúdez Ureña, Esteban; Huang, Gaoshan; Schmidt, Oliver G

    2009-07-01

    Strain-engineered microtubes with an inner catalytic surface serve as self-propelled microjet engines with speeds of up to approximately 2 mm s(-1) (approximately 50 body lengths per second). The motion of the microjets is caused by gas bubbles ejecting from one opening of the tube, and the velocity can be well approximated by the product of the bubble radius and the bubble ejection frequency. Trajectories of various different geometries are well visualized by long microbubble tails. If a magnetic layer is integrated into the wall of the microjet engine, we can control and localize the trajectories by applying external rotating magnetic fields. Fluid (i.e., fuel) pumping through the microtubes is revealed and directly clarifies the working principle of the catalytic microjet engines.

  7. Radiant non-catalytic recuperative reformer

    Energy Technology Data Exchange (ETDEWEB)

    Khinkis, Mark J.; Kozlov, Aleksandr P.

    2017-10-31

    A radiant, non-catalytic recuperative reformer has a flue gas flow path for conducting hot exhaust gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is positioned adjacent to the flue gas flow path to permit heat transfer from the hot exhaust gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, a portion of the reforming mixture flow path is positioned outside of flue gas flow path for a relatively large residence time.

  8. Chemical and catalytic effects of ion implantation

    International Nuclear Information System (INIS)

    Wolf, G.K.

    1982-01-01

    Energetic particles are used for inducing chemical reactions as well as for modifying the properties of materials with regard to their bulk and surface chemical behavior. The effects are partly caused by radiation damage or phase intermixing, partly by the chemical properties of the individual bombarding particles. In this contribution a survey of relevant applications of these techniques is presented: (1) Chemical reactions of implanted and recoil atoms and their use for syntheses, doping and labeling of compounds. (2) The formation of thin films by decomposing chemical compounds with ion beams. 3) Catalytic effects on substrates treated by sputtering or ion implantation. Recent results with nonmetallic substrates are reviewed. Mainly hydrogenation reactions at a solid/gas interface or redox reactions at an electrified solid/liquid interface are mentioned. The present status and future prospects of these kinds of investigations will be discussed. (author)

  9. Contact structure for use in catalytic distillation

    Science.gov (United States)

    Jones, E.M. Jr.

    1984-03-27

    A method is described for conducting catalytic chemical reactions and fractionation of the reaction mixture comprising feeding reactants into a distillation column reactor, contracting said reactant in liquid phase with a fixed bed catalyst in the form of a contact catalyst structure consisting of closed porous containers containing the catalyst for the reaction and a clip means to hold and support said containers, which are disposed above, i.e., on the distillation trays in the tower. The trays have weir means to provide a liquid level on the trays to substantially cover the containers. In other words, the trays function in their ordinary manner with the addition thereto of the catalyst. The reaction mixture is concurrently fractionated in the column. 7 figs.

  10. Catalytic hot gas cleaning of gasification gas

    Energy Technology Data Exchange (ETDEWEB)

    Simell, P. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1997-12-31

    The aim of this work was to study the catalytic cleaning of gasification gas from tars and ammonia. In addition, factors influencing catalytic activity in industrial applications were studied, as well as the effects of different operation conditions and limits. Also the catalytic reactions of tar and ammonia with gasification gas components were studied. The activities of different catalyst materials were measured with laboratory-scale reactors fed by slip streams taken from updraft and fluid bed gasifiers. Carbonate rocks and nickel catalysts proved to be active tar decomposing catalysts. Ammonia decomposition was in turn facilitated by nickel catalysts and iron materials like iron sinter and iron dolomite. Temperatures over 850 deg C were required at 2000{sup -1} space velocity at ambient pressure to achieve almost complete conversions. During catalytic reactions H{sub 2} and CO were formed and H{sub 2}O was consumed in addition to decomposing hydrocarbons and ammonia. Equilibrium gas composition was almost achieved with nickel catalysts at 900 deg C. No deactivation by H{sub 2}S or carbon took place in these conditions. Catalyst blocking by particulates was avoided by using a monolith type of catalyst. The apparent first order kinetic parameters were determined for the most active materials. The activities of dolomite, nickel catalyst and reference materials were measured in different gas atmospheres using laboratory apparatus. This consisted of nitrogen carrier, toluene as tar model compound, ammonia and one of the components H{sub 2}, H{sub 2}O, CO, CO{sub 2}, CO{sub 2}+H{sub 2}O or CO+CO{sub 2}. Also synthetic gasification gas was used. With the dolomite and nickel catalyst the highest toluene decomposition rates were measured with CO{sub 2} and H{sub 2}O. In gasification gas, however, the rate was retarded due to inhibition by reaction products (CO, H{sub 2}, CO{sub 2}). Tar decomposition over dolomite was modelled by benzene reactions with CO{sub 2}, H

  11. Smoke emissions from a catalytic wood stove

    International Nuclear Information System (INIS)

    Cowburn, D.A.; Stephens, N.P.J.

    1994-01-01

    The work reported here was concerned with testing a catalytic wood burning stove (roomheater) following the most applicable UK procedures. The identical stove has also been tested in several other nations to their individual procedures. The results will be submitted to the International Energy Agency (IEA) such that appropriate comparisons can be made. The results comprised: burning rate; an indicative appliance efficiency; heat output; carbon dioxide emissions; carbon monoxide emissions; and smoke emissions. These results were determined with the appliance at three nominal burning rates (high, medium and low). Comparing the results with those obtained in other countries indicates good agreement except when the appliance was operated at low burning rates, under which conditions the UK results indicate significantly worse smoke emissions than those measured by other researchers. (author)

  12. Flowthrough Reductive Catalytic Fractionation of Biomass

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Eric M.; Stone, Michael L.; Katahira, Rui; Reed, Michelle; Beckham, Gregg T.; Román-Leshkov, Yuriy

    2017-11-01

    Reductive catalytic fractionation (RCF) has emerged as a leading biomass fractionation and lignin valorization strategy. Here, flowthrough reactors were used to investigate RCF of poplar. Most RCF studies to date have been conducted in batch, but a flow-based process enables the acquisition of intrinsic kinetic and mechanistic data essential to accelerate the design, optimization, and scale-up of RCF processes. Time-resolved product distributions and yields obtained from experiments with different catalyst loadings were used to identify and deconvolute events during solvolysis and hydrogenolysis. Multi-bed RCF experiments provided unique insights into catalyst deactivation, showing that leaching, sintering, and surface poisoning are causes for decreased catalyst performance. The onset of catalyst deactivation resulted in higher concentrations of unsaturated lignin intermediates and increased occurrence of repolymerization reactions, producing high-molecular-weight species. Overall, this study demonstrates the concept of flowthrough RCF, which will be vital for realistic scale-up of this promising approach.

  13. Propulsion Mechanism of Catalytic Microjet Engines.

    Science.gov (United States)

    Fomin, Vladimir M; Hippler, Markus; Magdanz, Veronika; Soler, Lluís; Sanchez, Samuel; Schmidt, Oliver G

    2014-02-01

    We describe the propulsion mechanism of the catalytic microjet engines that are fabricated using rolled-up nanotech. Microjets have recently shown numerous potential applications in nanorobotics but currently there is a lack of an accurate theoretical model that describes the origin of the motion as well as the mechanism of self-propulsion. The geometric asymmetry of a tubular microjet leads to the development of a capillary force, which tends to propel a bubble toward the larger opening of the tube. Because of this motion in an asymmetric tube, there emerges a momentum transfer to the fluid. In order to compensate this momentum transfer, a jet force acting on the tube occurs. This force, which is counterbalanced by the linear drag force, enables tube velocities of the order of 100 μ m/s. This mechanism provides a fundamental explanation for the development of driving forces that are acting on bubbles in tubular microjets.

  14. Catalytic Synthesis of Nitriles in Continuous Flow

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine

    The objective of this thesis is to report the development of a new, alternative process for the flexible production of nitrile compounds in continuous flow. Nitriles are an important class of compounds that find applications as solvents, chemical intermediates and pharmaceutical compounds......, alternative path to acetonitrile from ethanol via the oxidative dehydrogenation of ethylamine. The catalytic activity and product ratios of the batch and continuous flow reactions are compared and the effect of reaction conditions on the reaction is investigated. The effects of ammonia in the reaction...... dehydrogenation of ethylamine and post-reaction purging.Chapter 4 outlines the application of RuO2/Al2O3 catalysts to the oxidative dehydrogenation of benzylamine in air, utilizing a new reaction setup. Again, batch and continuous flow reactions are compared and the effects of reaction conditions, ammonia...

  15. Soluble organic nanotubes for catalytic systems

    Science.gov (United States)

    Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

    2016-03-01

    In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core-shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the ‘confined effect’ and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

  16. Soluble organic nanotubes for catalytic systems.

    Science.gov (United States)

    Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

    2016-03-18

    In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core–shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the 'confined effect' and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

  17. Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

    KAUST Repository

    Imran, Ali; Bramer, Eddy A.; Seshan, Kulathuiyer; Brem, Gerrit

    2015-01-01

    Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two

  18. Catalytic combustion in small wood burning appliances

    Energy Technology Data Exchange (ETDEWEB)

    Oravainen, H. [VTT Energy, Jyvaeskylae (Finland)

    1996-12-31

    There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

  19. Catalytic combustion in small wood burning appliances

    Energy Technology Data Exchange (ETDEWEB)

    Oravainen, H [VTT Energy, Jyvaeskylae (Finland)

    1997-12-31

    There is over a million hand fired small heating appliances in Finland where about 5,4 million cubic meters of wood fuel is used. Combustion in such heating appliances is a batch-type process. In early stages of combustion when volatiles are burned, the formation of carbon monoxide (CO) and other combustible gases are difficult to avoid when using fuels that have high volatile matter content. Harmful emissions are formed mostly after each fuel adding but also during char burnout period. When the CO-content in flue gases is, say over 0.5 %, also other harmful emissions will be formed. Methane (CH{sub 4}) and other hydrocarbons are released and the amount of polycyclic aromatic hydrocarbons (PAH)-compounds can be remarkable. Some PAH-compounds are very carcinogenic. It has been estimated that in Finland even more than 90 % of hydrocarbon and PAH emissions are due to small scale wood combustion. Emissions from transportation is excluded from these figures. That is why wood combustion has a net effect on greenhouse gas phenomena. For example carbon monoxide emissions from small scale wood combustion are two fold compared to that of energy production in power plants. Methane emission is of the same order as emission from transportation and seven fold compared with those of energy production. Emissions from small heating appliances can be reduced by developing the combustion techniques, but also by using other means, for example catalytic converters. In certain stages of the batch combustion, temperature is not high enough, gas mixing is not good enough and residence time is too short for complete combustion. When placed to a suitable place inside a heating appliance, a catalytic converter can oxidize unburned gases in the flue gas into compounds that are not harmful to the environment. (3 refs.)

  20. Thermodynamic Analysis of an Integrated Solid Oxide Fuel Cell Cycle with a Rankine Cycle

    DEFF Research Database (Denmark)

    Rokni, Masoud

    2010-01-01

    Hybrid systems consisting of Solid Oxide Fuel Cells (SOFC) on the top of a Steam Turbine (ST) are investigated. The plants are fired by natural gas (NG). A desulfurization reactor removes the sulfur content in the fuel while a pre-reformer breaks down the heavier hydrocarbons. The pre-treated fuel......% are achieved which is considerably higher than the conventional Combined Cycles (CC). Both ASR (Adiabatic Steam Reformer) and CPO (Catalytic Partial Oxidation) fuel pre-reformer reactors are considered in this investigation....