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Sample records for catalytic partial oxidation

  1. Catalytic partial oxidation of pyrolysis oils

    Science.gov (United States)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  2. Catalytic Partial Oxidation of Biomass/Oil Mixture

    Czech Academy of Sciences Publication Activity Database

    Veselý, Václav; Hanika, Jiří; Tukač, V.; Lederer, J.; Kovač, D.

    2013-01-01

    Roč. 7, č. 10 (2013), s. 1940-1945 ISSN 1934-8983 R&D Projects: GA TA ČR TE01020080; GA MPO 2A-2TP1/024 Institutional support: RVO:67985858 Keywords : hydrocarbon oil * biomass * catalytic partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.davidpublishing.com/journals_info.asp?jId=1718#

  3. Catalytic partial oxidation of methanol and ethanol for hydrogen generation.

    Science.gov (United States)

    Hohn, Keith L; Lin, Yu-Chuan

    2009-01-01

    Hydrogen-powered fuel cell vehicles feature high energy efficiency and minor environmental impact. Liquid fuels are ideal hydrogen carriers, which can catalytically be converted into syngas or hydrogen to power vehicles. Among the potential liquid fuels, alcohols have several advantages. The hydrogen/carbon ratio is higher than that of other liquid hydrocarbons or oxygenates, especially in the case of methanol. In addition, alcohols can be derived from renewable biomass resources. Catalytic partial oxidation of methanol or ethanol offers immense potential for onboard hydrogen generation due to its rapid reaction rate and exothermic nature. These benefits stimulate a burgeoning research community in catalyst design, reaction engineering, and mechanistic investigation. The purpose of this Minireview is to provide insight into syngas and hydrogen production from methanol and ethanol partial oxidation, particularly highlighting catalytic chemistry.

  4. Dual catalyst bed concept for catalytic partial oxidation of methane to synthesis gas

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    A system with two catalyst beds instead of one single metal catalyst bed is proposed for catalytic partial oxidation of methane (CPOM) to synthesis gas. In this dual catalyst bed system, an irreducible stable oxide, such as yttrium-stabilized zirconia (YSZ), is used in the first catalyst bed to

  5. Comparison Of Different Noble Metal Catalysts For The Low Temperature Catalytic Partial Oxidation Of Methane

    Energy Technology Data Exchange (ETDEWEB)

    Rabe, S.; Truong, T.-B.; Vogel, F.

    2005-03-01

    The generation of synthesis gas at low temperatures can contribute to a more economic production of clean transportation fuels (Fischer-Tropsch liquids) from natural gas. In this report, the performance of different noble metal catalysts in a low temperature catalytic partial oxidation process is presented. (author)

  6. Oscillatory Behavior during the Catalytic Partial Oxidation of Methane: Following Dynamic Structural Changes of Palladium Using the QEXAFS Technique

    DEFF Research Database (Denmark)

    Stoetzel, Jan; Frahm, Ronald; Kimmerle, Bertram

    2012-01-01

    as a combination of total oxidation and reforming in the catalytic capillary reactor was observed. This change in catalytic performance was directly linked to changes in the oxidation state of the Pd/Al2O3 catalysts at different positions along the catalytic reactor. During the ignition of the catalytic partial......Pd/Al2O3 catalysts oscillate between ignition and extinction of the catalytic partial oxidation of methane when they are exposed to a 2:1 reaction mixture of methane and oxygen. The oscillations of the catalytic performance and the structure of Pd/Al2O3 catalysts in a fixed-bed reactor were...... by the oven temperature than the ignition behavior of the catalytic partial oxidation of methane. This indicates that deactivation is caused by an autoreduction of the palladium at the beginning of the catalyst bed due to the high temperature achieved by total oxidation of methane....

  7. Synthesis gas production via catalytic partial oxidation reforming of liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Cheekatamarla, P.K.; Finnerty, C.M. [NanoDynamics Energy Inc., 901 Fuhrmann Boulevard, Buffalo, NY 14203 (United States)

    2008-10-15

    This work deals with the performance of waterless catalytic partial oxidation (CPOX)-based catalytic reformer system fed by different liquid fuels including ethanol, isooctane, hexadecane, synthetic JP8, kerosene and diesel for solid oxide fuel cell applications. The effect of different fuel components on product composition was studied and the operational parameters were optimized to provide a stable reforming performance. The system provided negligible pressure drop combined with the simpler system design due to the lack of water requirement making the POX reformer an attractive choice. (author)

  8. Visualizing a Catalyst at Work during the Ignition of the Catalytic Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Kimmerle, Bertram; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2009-01-01

    We present a spatiotemporal operando X-ray absorption study of a highly dynamic process, the ignition of the noble metal catalyzed partial oxidation of methane. Evolvement and propagation of the platinum component's structural changes are investigated with a high-speed X-ray camera, which in comb...... in combination with temperature profiling by IR-thermography and catalytic activity measurements by online mass spectrometry gives insight into the first stages of the ignition of the reaction toward hydrogen and carbon monoxide....

  9. 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)

  10. Oscillatory behaviour of catalytic properties, structure and temperature during the catalytic partial oxidation of methane on Pd/Al2O3

    DEFF Research Database (Denmark)

    Kimmerle, B.; Baiker, A.; Grunwaldt, Jan-Dierk

    2010-01-01

    Pd/Al2O3 catalysts showed an oscillatory behaviour during the catalytic partial oxidation (CPO) of methane, which was investigated simultaneously by IR-thermography, X-ray absorption spectroscopy, and online mass-spectrometry to correlate the temperature, state of the catalyst and catalytic...... to self-reduction leading to extinction of the process. The latter was the key driver for the oscillations and thus gave additional insight into the mechanism of partial methane oxidation....

  11. Catalytic partial oxidation coupled with membrane purification to improve resource and energy efficiency in syngas production.

    Science.gov (United States)

    Iaquaniello, G; Salladini, A; Palo, E; Centi, G

    2015-02-01

    Catalytic partial oxidation coupled with membrane purification is a new process scheme to improve resource and energy efficiency in a well-established and large scale-process like syngas production. Experimentation in a semi industrial-scale unit (20 Nm(3)  h(-1) production) shows that a novel syngas production scheme based on a pre-reforming stage followed by a membrane for hydrogen separation, a catalytic partial oxidation step, and a further step of syngas purification by membrane allows the oxygen-to-carbon ratio to be decreased while maintaining levels of feed conversion. For a total feed conversion of 40 %, for example, the integrated novel architecture reduces oxygen consumption by over 50 %, with thus a corresponding improvement in resource efficiency and an improved energy efficiency and economics, these factors largely depending on the air separation stage used to produce pure oxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Catalytic partial oxidation of methane over porous silica supported VO{sub x} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Pirovano, C.; Schoenborn, E.; Kalevaru, V.N.; Wohlrab, S.; Luecke, B.; Martin, A. [University Rostock e.V., Rostock (Germany). Leibniz Inst. for Catalysis

    2011-07-01

    High surface area mesoporous siliceous MCM-41 and SBA-15 materials have been used as supports to disperse vanadium oxide species using wet impregnation and incipient wetness impregnation methods. These materials were used as catalysts for the partial oxidation of methane (POM) to formaldehyde. The physico-chemical properties of the solids were studied by means of BET, DR-UV/Vis spectroscopy, Py-FTIR and TEM. The influence of support and the preparation method on the dispersion of VOx is also investigated. The catalytic properties of the catalysts were examined in a fixed bed stainless steel reactor at 923 K. So far a maximum production of formaldehyde can be detected on SBA-15 supported VOx-catalysts prepared by incipient wetness impregnation. On this V/SBA-15 material a covalent attachment of catalytic active molecular vanadium species dominates, which in turn leads to a lower activation temperature and thereby reduced over-oxidation. From the best case, the space time yield of HCHO could be reached close to 775 g{sub HCHO} Kg{sub cat}{sup -1} h{sup -1}. (orig.)

  13. Integrated Biomass Gasification with Catalytic Partial Oxidation for Selective Tar Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lingzhi; Wei, Wei; Manke, Jeff; Vazquez, Arturo; Thompson, Jeff; Thompson, Mark

    2011-05-28

    requirement for commercial deployment of biomass-based power/heat co-generation and biofuels production. There are several commonly used syngas clean-up technologies: (1) Syngas cooling and water scrubbing has been commercially proven but efficiency is low and it is only effective at small scales. This route is accompanied with troublesome wastewater treatment. (2) The tar filtration method requires frequent filter replacement and solid residue treatment, leading to high operation and capital costs. (3) Thermal destruction typically operates at temperatures higher than 1000oC. It has slow kinetics and potential soot formation issues. The system is expensive and materials are not reliable at high temperatures. (4) In-bed cracking catalysts show rapid deactivation, with durability to be demonstrated. (5) External catalytic cracking or steam reforming has low thermal efficiency and is faced with problematic catalyst coking. Under this program, catalytic partial oxidation (CPO) is being evaluated for syngas tar clean-up in biomass gasification. The CPO reaction is exothermic, implying that no external heat is needed and the system is of high thermal efficiency. CPO is capable of processing large gas volume, indicating a very compact catalyst bed and a low reactor cost. Instead of traditional physical removal of tar, the CPO concept converts tar into useful light gases (eg. CO, H2, CH4). This eliminates waste treatment and disposal requirements. All those advantages make the CPO catalytic tar conversion system a viable solution for biomass gasification downstream gas clean-up. This program was conducted from October 1 2008 to February 28 2011 and divided into five major tasks. - Task A: Perform conceptual design and conduct preliminary system and economic analysis (Q1 2009 ~ Q2 2009) - Task B: Biomass gasification tests, product characterization, and CPO tar conversion catalyst preparation. This task will be conducted after completing process design and system economics analysis

  14. Operating envelope of a short contact time fuel reformer for propane catalytic partial oxidation

    Science.gov (United States)

    Waller, Michael G.; Walluk, Mark R.; Trabold, Thomas A.

    2015-01-01

    Fuel cell technology has yet to realize widespread deployment, in part because of the hydrogen fuel infrastructure required for proton exchange membrane systems. One option to overcome this barrier is to produce hydrogen by reforming propane, which has existing widespread infrastructure, is widely used by the general public, easily transported, and has a high energy density. The present work combines thermodynamic modeling of propane catalytic partial oxidation (cPOx) and experimental performance of a Precision Combustion Inc. (PCI) Microlith® reactor with real-time soot measurement. Much of the reforming research using Microlith-based reactors has focused on fuels such as natural gas, JP-8, diesel, and gasoline, but little research on propane reforming with Microlith-based catalysts can be found in literature. The aim of this study was to determine the optimal operating parameters for the reformer that maximizes efficiency and minimizes solid carbon formation. The primary parameters evaluated were reformate composition, carbon concentration in the effluent, and reforming efficiency as a function of catalyst temperature and O2/C ratio. Including the lower heating values for product hydrogen and carbon monoxide, efficiency of 84% was achieved at an O2/C ratio of 0.53 and a catalyst temperature of 940 °C, resulting in near equilibrium performance. Significant solid carbon formation was observed at much lower catalyst temperatures, and carbon concentration in the effluent was determined to have a negative linear relationship at T reactor displayed good stability during more than 80 experiments with temperature cycling from 360 to 1050 °C.

  15. Basic promoters effect over nickel/alumina catalyst on hydrogen production via methane catalytic partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Requies, J.; Cabrero, M. A.; Barrio, V. I.; Cambra, J. F.; Arias, P. L.; Guemez, B.; La Oarola, V.; Pena, M. A.; Fierro, J. L. G.

    2005-07-01

    The European Directives concerning the environment protection and the sustainable development include the green fuels production and utilization. Thus, one of their major objectives is related to the research on processes to obtain green fuels and their direct application or their transformation in clean energy carriers and final fuels as hydrogen. Hydrogen is an energy vector that is being considered by most countries and many energy companies as a possible long-term solution in the electricity, heating and transport energy markets, where it will offer greenhouse gas abatement and other local air quality benefits. Before the generalization of hydrogen production from renewable resources, other production processes can fulfil the objective of generating an energy infrastructure based on hydrogen. By the methane catalytic partial oxidation (CPO) process or by an analogous one, like Wet CPO, a synthesis gas can be produced. This gas can be further treated to maximize the hydrogen production or it can also be used to generate clean liquid fuels precursors via Fischer-Tropsch synthesis. In the present work, the hydrogen and/or synthesis gas production via CPO or Wet-CPO is studied using nickel catalyst supported on -Al2O3 promoted by basic metals (Ca and Mg). The conventional nickel supported catalysts are highly effective for these processes. Nevertheless, they are unsatisfactory with respect to coke formation. Deactivation of these catalysts by a coke formation is sometimes a serious limitation. The addition of calcium and magnesium onto Ni/ -Al2O3 aims to eliminate the coke formation, via a reduction on support acidity, and as a result to improve these catalysts performance. The catalysts were prepared by consecutive wet impregnation method, and -Al2O3 was employed as acid support. The nominal contents of nickel were 15 and 25 wt%. The nominal contents of promoters were 5 and 10 wt% of Mg or Ca. The catalyst textural characterization was studied using different

  16. Catalytic Partial Oxidation of Cyclohexane by Bimetallic Ag/Pd Nanoparticles on Magnesium Oxide.

    Science.gov (United States)

    Liu, Xi; Conte, Marco; He, Qian; Knight, David W; Murphy, Damien M; Taylor, Stuart H; Whiston, Keith; Kiely, Christopher J; Hutchings, Graham J

    2017-09-04

    The liquid-phase oxidation of cyclohexane to cyclohexanol and cyclohexanone was investigated by synthesizing and testing an array of heterogeneous catalysts comprising: monometallic Ag/MgO, monometallic Pd/MgO and a set of bimetallic AgPd/MgO catalysts. Interestingly, Ag/MgO was capable of a conversion comparable to current industrial routes of approximately 5 %, and with a high selectivity (up to 60 %) to cyclohexanol, thus making Ag/MgO an attractive system for the synthesis of intermediates for the manufacture of nylon fibres. Furthermore, following the doping of Ag nanoparticles with Pd, the conversion increased up to 10 % whilst simultaneously preserving a high selectivity to the alcohol. Scanning transmission electron microscopy and energy dispersive spectroscopy of the catalysts showed a systematic particle-size-composition variation with the smaller Ag-Pd nanoparticles being statistically richer in Pd. Analysis of the reaction mixture by electron paramagnetic resonance (EPR) spectroscopy coupled with the spin-trapping technique showed the presence of large amounts of alkoxy radicals, thus providing insights for a possible reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Modelling of a reverse flow catalytic membrane reactor for the partial oxidation of methane

    NARCIS (Netherlands)

    Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

    2003-01-01

    Gas-To-Liquid (GTL) processes have great potential as alternative to conventional oil and coal processing for the production of liquid fuels. In GTL-processes the partial oxidation of methane (POM) is combined with the Fischer-Tropsch reaction. An important part of the investment costs of a

  18. Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions.

    Science.gov (United States)

    Bartling, Stephan; Yin, Chunrong; Barke, Ingo; Oldenburg, Kevin; Hartmann, Hannes; von Oeynhausen, Viola; Pohl, Marga-Martina; Houben, Kelly; Tyo, Eric C; Seifert, Sönke; Lievens, Peter; Meiwes-Broer, Karl-Heinz; Vajda, Stefan

    2015-06-23

    It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here, we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced and partially oxidized cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 and 22 nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case, the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate, an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

  19. Catalytic partial oxidation and membrane separation to optimize the conversion of natural gas to syngas and hydrogen.

    Science.gov (United States)

    Capoferri, Daniela; Cucchiella, Barbara; Iaquaniello, Gaetano; Mangiapane, Alessia; Abate, Salvatore; Centi, Gabriele

    2011-12-16

    The multistep integration of hydrogen-selective membranes into catalytic partial oxidation (CPO) technology to convert natural gas into syngas and hydrogen is reported. An open architecture for the membrane reactor is presented, in which coupling of the reaction and hydrogen separation is achieved independently and the required feed conversion is reached through a set of three CPO reactors working at 750, 750 and 920 °C, compared to 1030 °C for conventional CPO technology. Obtaining the same feed conversion at milder operating conditions translates into less natural gas consumption (and CO(2) emissions) and a reduction of variable operative costs of around 10 %. It is also discussed how this energy-efficient process architecture, which is suited particularly to small-to-medium applications, may improve the sustainability of other endothermic, reversible reactions to form hydrogen. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Reaction phenomena of catalytic partial oxidation of methane under the impact of carbon dioxide addition and heat recirculation

    International Nuclear Information System (INIS)

    Chen, Wei-Hsin; Lin, Shih-Cheng

    2015-01-01

    The reaction phenomena of CPOM (catalytic partial oxidation of methane) in a Swiss-roll reactor are studied numerically where a rhodium-based catalyst bed is embedded at the center of the reactor. CO 2 is added into the feed gas and excess enthalpy recovery is performed to evaluate their influences on CPOM performance. In the study, the mole ratio of O 2 to CH 4 (O 2 /CH 4 ratio) is fixed at 0.5 and the mole ratio of CO 2 to O 2 (CO 2 /O 2 ratio) is in the range of 0–2. The results reveal that CO 2 addition into the influent has a slight effect on methane combustion, but significantly enhances dry reforming and suppresses steam reforming. The reaction extents of steam reforming and dry reforming in CPOM without heat recovery and CO 2 addition are in a comparable state. Once CO 2 is added into the feed gas, the dry reforming is enhanced, thereby dominating CH 4 consumption. Compared to the reactor without excess enthalpy recovery, heat recirculation drastically increases the maximum reaction temperature and CH 4 conversion in the catalyst bed; it also intensifies the H 2 selectivity, H 2 yield, CO 2 conversion, and syngas production rate. The predictions indicate that the heat recirculation is able to improve the syngas formation up to 45%. - Highlights: • Catalytic partial oxidation of methane with CO 2 addition and heat recovery is studied. • CO 2 addition has a slight effect on methane combustion. • CO 2 addition significantly enhances dry reforming and suppresses steam reforming. • Dry reforming dominates CH 4 consumption when CO 2 addition is large. • Heat recirculation can improve the syngas formation up to 45%

  1. Effect of redox additives over Ni/Al{sub 2}O{sub 3} catalysts on syngas production via methane catalytic partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    J. Requies; V.L. Barrio; J.F. Cambra; M.B. Guemez; P.L. Arias; V. La Parola; M.A. Pena; J.L.G. Fierro [University of the Basque Country, Bilbao (Spain). School of Engineering

    2008-11-15

    Alumina-supported nickel catalysts modified with redox (Mo, Mn and Sn) oxides were tested in the catalytic partial oxidation (CPO) of methane and the wet catalytic partial oxidation (wet-CPO) of methane for syngas production. The influence of different reaction parameters on the performance of these systems was studied for both reactions. Certain insights on catalyst surface structure were revealed by means of X-ray photoelectron spectroscopy (XPS) and thermal programmed reduction (TPR). The joint analysis of all the results led to certain correlations between the structure of the catalysts and catalytic activity, indicating that the redox additives to some extent modify the stability of the active nickel phase by altering the nickel-alumina interface interaction. 37 refs., 9 figs., 4 tabs.

  2. Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Bartling, Stephan; Yin, Chunrong; Barke, Ingo; Oldenburg, Kevin; Hartmann, Hannes; von Oeynhausen, Viola; Pohl, Marga-Martina; Houben, Kelly; Tyo, Eric C.; Seifert, Sönke; Lievens, Peter; Meiwes-Broer, Karl-Heinz; Vajda, Stefan

    2015-06-23

    It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 nm and 22nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

  3. Experimental and numerical investigation of the catalytic partial oxidation of methane to synthesis gas for power generation applications[Dissertation 17183

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, A.

    2007-07-01

    The present work addresses the catalytic partial oxidation (CPO) of methane to synthesis gas, with particular emphasis on power generation applications. A combined experimental and numerical investigation of methane partial oxidation to synthesis gas (H{sub 2}, CO) over rhodium-based catalysts has been carried out at pressures of up to 10 bar. The reactivity of the produced hydrogen and the suitably-low light-off temperatures of the CPO reactor, greatly facilitate operation of power generation gas turbines with reduced NO{sub x} emissions, stable operation with low calorific value fuels, and new combustion strategies for efficient CO{sub 2} capture. Those strategies utilize CPO of methane with oxygen (separated from air) and large exhaust gas recycle (H{sub 2}O and CO{sub 2}). An optically accessible catalytic channel-flow reactor was used to carry out Raman spectroscopy of major gas-phase species and laser induced fluorescence (LIF) of formaldehyde, in order to gain fundamental information on the catalytic and gas-phase chemical pathways. Transverse concentration profiles measured by the spontaneous Raman scattering technique determined the catalytic reactivity, while the LIF provided flame shapes and anchoring positions that, in turn, characterized the gaseous reactivity. Comparison between measurements and 2-D CFD computations, led to the validation of detailed catalytic and gas-phase reaction mechanisms. Experiments in a subscale gas-turbine honeycomb catalytic reactor have shown that the foregoing reaction mechanisms were also appropriate under gas-turbine relevant conditions with short reactant residence times. The light-off behavior of the subscale honeycomb reactor was reproduced by transient 2-D CFD computations. Ignition and extinction in CPO was studied. It was shown that, despite the chemical impact of the H{sub 2}O diluent during the transient catalytic ignition event, the light-off times themselves were largely unaffected by the exhaust gas dilution

  4. Catalytic Activity Studies of Vanadia/Silica–Titania Catalysts in SVOC Partial Oxidation to Formaldehyde: Focus on the Catalyst Composition

    Directory of Open Access Journals (Sweden)

    Niina Koivikko

    2018-02-01

    Full Text Available In this work, silica–titania supported catalysts were prepared by a sol–gel method with various compositions. Vanadia was impregnated on SiO2-TiO2 with different loadings, and materials were investigated in the partial oxidation of methanol and methyl mercaptan to formaldehyde. The materials were characterized by using N2 physisorption, X-ray diffraction (XRD, X-ray fluorescence spectroscopy (XRF, X-ray photoelectron spectroscopy (XPS, Scanning transmission electron microscope (STEM, NH3-TPD, and Raman techniques. The activity results show the high importance of an optimized SiO2-TiO2 ratio to reach a high reactant conversion and formaldehyde yield. The characteristics of mixed oxides ensure a better dispersion of the active phase on the support and in this way increase the activity of the catalysts. The addition of vanadium pentoxide on the support lowered the optimal temperature of the reaction significantly. Increasing the vanadia loading from 1.5% to 2.5% did not result in higher formaldehyde concentration. Over the 1.5%V2O5/SiO2 + 30%TiO2 catalyst, the optimal selectivity was reached at 415 °C when the maximum formaldehyde concentration was ~1000 ppm.

  5. Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane.

    Science.gov (United States)

    Li, Hongliang; Wang, Renzhang; Hong, Qi; Chen, Luwei; Zhong, Ziyi; Koltypin, Yuri; Calderon-Moreno, J; Gedanken, Aharon

    2004-09-14

    Metallic Ru nanoparticles have been successfully produced and incorporated into the pores of SBA-15 in situ employing a simple ultrasound-assisted polyol method. The product has been confirmed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy, where ultrasound provides both the energy for the reduction of the Ru(III) ion and the driving force for the loading of the Ru(0) nanoparticles into the SBA-15 pores. An ultrasound-assisted insertion mechanism has been proposed based on the microjets and shake-wave effect of the collapsed bubbles. The catalytic properties of the SBA-15-supported Ru nanoparticles have been tested by the partial oxidization of methane and show very high activity and high CO selectivity.

  6. The Relationship Between Structural and Catalytic Activity of α and γ-Bismuth-Molybdate Catalysts for Partial Oxidation of Propylene to Acrolein

    Science.gov (United States)

    Fansuri, H.; Pham, G. H.; Wibawanta, S.; Zhang, D. K.; French, David

    Bismuth-molybdate catalysts are known to be effective for catalytic partial oxidation of propylene to acrolein. Their properties and the kinetics and reaction mechanisms for acrolein production have been extensively studied, especially in their basic forms, such as α, β, and γ-bismuth-molybdate. Although the reaction mechanisms have been reported widely in the literature, a general agreement has not been reached, especially from a catalyst-structure point of view. The present contribution reports an effort to understand the structural changes of α and γ-bismuth-molybdate catalysts at varying temperatures as examined using high temperature XRD and to relate the catalyst performance (activity and selectivity) for propylene partial oxidation to acrolein. The XRD analysis was performed at temperature between 250 and 450°C in ambient atmosphere and the Rietveld refinement method was used to extract unit cell parameters. The results showed a distinct similarity between the shapes of the thermal expansion of the catalysts and their activity and selectivity curves, indicating a significant role that the catalyst interatomic structure plays in the overall reaction mechanism.

  7. Reactor modeling to simulate catalytic partial oxidation and steam reforming of methane. Comparison of temperature profiles and strategies for hot spot minimization

    Energy Technology Data Exchange (ETDEWEB)

    Barrio, V.L.; Cambra, J.F.; Arias, P.L.; Gueemez, M.B. [School of Engineering (UPV/EHU), c/Alameda Urquijo s/n, 48013 Bilbao (Spain); Schaub, G.; Rohde, M. [Engler-Bunte-Institut, Universitaet Karlsruhe, Engler-Bunte-Ring 1, 76131 Karlsruhe (Germany); Rabe, S.; Vogel, F. [Paul Scherrer Institute, Laboratory for Energy and Materials Cycles, CH-5232 Villigen PSI (Switzerland)

    2007-07-15

    Catalytic partial oxidation (CPO) reactions of methane in the presence of steam (low temperature CPO, LTCPO) over a noble metal catalyst were investigated. A quasi-homogeneous one-dimensional model was developed in order to model a lab-scale fixed-bed reactor to produce syngas. These model calculations can contribute to the optimization of the process with respect to the formation of important hot spots ({delta} T{>=}130 ). These useful data can enable the model development in order to study the influence of the space velocity, product composition and other variables. Furthermore, a feed splitting study was performed. In the heat balance an overall heat transport term was included to account for small heat losses/gains along the reactor. The agreement between simulations and the degree of detail in the model is appropriate for the amount and kind of experimental data available. Thus, this model can also assist in a pilot reactor design, materials and further scale-up. (author)

  8. Methanol partial oxidation reformer

    Science.gov (United States)

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  9. CATALYTIC ENANTIOSELECTIVE ALLYLIC OXIDATION

    NARCIS (Netherlands)

    Rispens, Minze T.; Zondervan, Charon; Feringa, Bernard

    Several chiral Cu(II)-complexes of cyclic amino acids catalyse the enantioselective allylic oxidation of cyclohexene to cyclohexenyl esters. Cyclohexenyl propionate was obtained in 86% yield with e.e.'s up to 61%.

  10. SYNTHESIZING ALCOHOLS AND KETONES BY PHOTOINDUCED CATALYTIC PARTIAL-OXIDATION OF HYDROCARBONS IN TI02 FILM REACTORS PREPARED BY THREE DIFFERENT METHODS

    Science.gov (United States)

    The partial oxidation of cyclohexane to cyclohexanol and cyclohexanone on UV irradiated titanium dioxide films in the presence of molecular oxygen at ambient temperatures and pressures was studied. Three different coating methodologies (dip coating using titanium isopropoxide an...

  11. Hydrogen production with short contact time. Catalytic partial oxidation of hydrocarbons and oxygenated compounds: Recent advances in pilot- and bench-scale testing and process design

    Energy Technology Data Exchange (ETDEWEB)

    Guarinoni, A.; Ponzo, R.; Basini, L. [ENI Refining and Marketing Div., San Donato Milanese (Italy)

    2010-12-30

    ENI R and D has been active for fifteen years in the development of Short Contact Time - Catalytic Partial Oxidation (SCT-CPO) technologies for producing Hydrogen/Synthesis Gas. From the beginning the experimental work addressed either at defining the fundamental principles or the technical and economical potential of the technology. Good experimental responses, technical solutions' simplicity and flexibility, favourable techno-economical evaluations promoted the progressive widening of the field of the investigations. From Natural Gas (NG) the range of ''processable'' Hydrocarbons extended to Liquefied Petroleum Gas (LPG) and Gasoils, including those characterised by high levels of unsaturated and sulphurated molecules and, lately, to other compounds with biological origin. The extensive work led to the definition of different technological solutions, grouped as follows: Technology 1: Air Blown SCT-CPO of Gaseous Hydrocarbons and/or Light Compounds with biological origin Technology 2: Enriched Air/Oxygen Blown SCT-CPO of Gaseous Hydrocarbons and/or Light Compounds with biological origin Technology 3: Enriched Air/Oxygen Blown SCT-CPO of Liquid Hydrocarbons and/or Compounds with biological origin Recently, the licence rights on a non-exclusive basis for the commercialisation of SCT-CPO based processes for H{sub 2}/Synthesis gas production from light hydrocarbons with production capacity lower than 5,000 Nm{sup 3}/h of H{sub 2} or 7,500 Nm3/h of syngas have been assigned to two external companies. In parallel, development of medium- and large-scale plant solutions is progressing within the ENI group framework. These last activities are addressed to the utilisation of SCT-CPO for matching the variable Hydrogen demand in several contexts of oil refining operation. This paper will report on the current status of SCT-CPO with a focus on experimental results obtained, either at pilot- and bench- scale level. (orig.)

  12. 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.)

  13. Partial oxidation of 2-propanol on perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Sumathi, R.; Viswanathan, B.; Varadarajan, T.K. [Indian Inst. of Tech., Madras (India). Dept. of Chemistry

    1998-12-31

    Partial oxidation of 2-propanol was carried out on AB{sub 1-x}B`{sub x}O{sub 3} (A=Ba, B=Pb, Ce, Ti; B`=Bi, Sb and Cu) type perovskite oxides. Acetone was the major product observed on all the catalysts. All the catalysts underwent partial reduction during the reaction depending on the composition of the reactant, nature of the B site cation and the extent of substitution at B site. The catalytic activity has been correlated with the reducibility of the perovskite oxides determined from Temperature Programmed Reduction (TPR) studies. (orig.)

  14. Ni-doped (CeO2- δ )-YSZ mesoarchitectured with nanocrystalline framework: the effect of thermal treatment on structure, surface chemistry and catalytic properties in the partial oxidation of methane (CPOM)

    Science.gov (United States)

    Somacescu, Simona; Florea, Mihaela; Osiceanu, Petre; Calderon-Moreno, Jose Maria; Ghica, Corneliu; Serra, Jose Manuel

    2015-11-01

    Ni-doped (CeO2- δ )-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure ( 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer—Emmett—Teller, BET; Temperature—Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N2 sorption measurements highlighted that the mesoporous structure is formed at 600 °C and remains stable at 800 °C. At 900 °C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 °C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.

  15. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones

    2011-03-31

    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  16. Rh promoted La0.75Sr0.25(Fe0.8Co0.2)1−xGaxO3-δ perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

    International Nuclear Information System (INIS)

    Palcheva, R.; Olsbye, U.; Palcut, M.; Rauwel, P.; Tyuliev, G.; Velinov, N.; Fjellvåg, H.H.

    2015-01-01

    Graphical abstract: - Highlights: • Perovskites type-oxide La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) prepared by the sol–gel citrate method. • Bulk and surface analysis to determine catalysts composition evolution. • Anaerobic catalytic partial oxidation of methane to syngas at 600 °C in a pulse apparatus over Rh promoted perovskites. • The catalysts showed high stability and selectivity. - Abstract: Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol–gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H 2 ), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H 2 , as confirmed by XRD. Data of MS identified Fe 3+ ions in two distinctive coordination environments, and Fe 4+ ions. The Rh 2 O 3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H 2 , and surface carbon, CO 2 and H 2 O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La 0.75 Sr 0.25 (Fe 0.8 Co 0.2 ) 1−x Ga x O 3-δ perovskite materials.

  17. Catalytic wet oxidation of black liquor

    OpenAIRE

    Viader Riera, Gerard

    2012-01-01

    The major aspects of wet air oxidation and catalytic wet air oxidation have been reviewed in this work paying special attention to the reaction mechanisms, kinetics and the industrial process. In the experimental section a set of heterogeneous catalysts have been tested in the wet oxidation of non-wood black liquor. The oxidation runs were performed batchwise in a laboratory-scale mechanically stirred slurry reactor for 1 h at a temperature of 170°C and total pressure of 12 bar. Pure oxygen w...

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

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Synthesis, spectroscopic characterization and catalytic oxidation properties of ONO/ONS donor Schiff base ruthenium(III) complexes containing PPh3/AsPh3. Priyarega M Muthu Tamizh R Karvembu R Prabhakaran K Natarajan. Volume 123 Issue 3 May ...

  19. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  20. 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.

  1. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren

    The research interests in biomass conversion to fuels and chemicals has increased significantly in the last decade in view of current problems such as global warming, high oil prices, food crisis and other geopolitical scenarios. Many different reactions and processes to convert biomass into high......-value products and fuels have been proposed in the literature, giving special attention to the conversion of lignocellulosic biomass, which does not compete with food resources and is widely available as a low cost feedstock 1. Lignocellulose biomass is a complex material composed of three main fractions...... be obtained 2. Heiko Lange et al., has reported that the catalytic oxidation products of lignin and lignin model compounds range from aromatic aldehyde and carboxylic acid and they must be originate form oxidation of side chain. The products we obtained in these reactions are based on the severity...

  2. 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...

  3. Catalytic Reactor For Oxidizing Mercury Vapor

    Science.gov (United States)

    Helfritch, Dennis J.

    1998-07-28

    A catalytic reactor (10) for oxidizing elemental mercury contained in flue gas is provided. The catalyst reactor (10) comprises within a flue gas conduit a perforated corona discharge plate (30a, b) having a plurality of through openings (33) and a plurality of projecting corona discharge electrodes (31); a perforated electrode plate (40a, b, c) having a plurality of through openings (43) axially aligned with the through openings (33) of the perforated corona discharge plate (30a, b) displaced from and opposing the tips of the corona discharge electrodes (31); and a catalyst member (60a, b, c, d) overlaying that face of the perforated electrode plate (40a, b, c) opposing the tips of the corona discharge electrodes (31). A uniformly distributed corona discharge plasma (1000) is intermittently generated between the plurality of corona discharge electrode tips (31) and the catalyst member (60a, b, c, d) when a stream of flue gas is passed through the conduit. During those periods when corona discharge (1000) is not being generated, the catalyst molecules of the catalyst member (60a, b, c, d) adsorb mercury vapor contained in the passing flue gas. During those periods when corona discharge (1000) is being generated, ions and active radicals contained in the generated corona discharge plasma (1000) desorb the mercury from the catalyst molecules of the catalyst member (60a, b, c, d), oxidizing the mercury in virtually simultaneous manner. The desorption process regenerates and activates the catalyst member molecules.

  4. Hydrogen Production by Catalytic Partial Oxidation of Coke Oven Gas in BaCo0.7Fe0.3-xZrxO3-δ Ceramic Membrane Reactors

    Directory of Open Access Journals (Sweden)

    Yao Weilin

    2016-01-01

    Full Text Available The BaCo0.7Fe0.3-xZrxO3-δ (BCFZ, x = 0.04–0.12 mixed ionic–electronic conducting (MIEC membranes were synthesized with a sol–gel method and evaluated as potential membrane reactor materials for the partial oxidation of coke oven gas (COG. The effect of zirconium content on the phase structure, microstructure and performance of the BCFZ membrane under He or COG atmosphere were systemically investigated. The BaCo0.7Fe0.24Zr0.06O3-δ membrane exhibited the best oxygen permeability and good operation stability, which could be a potential candidate of the membrane materials for hydrogen production through the partial oxidation of COG.

  5. Steam reforming, partial oxidation, and oxidative steam reforming of ethanol over Pt/CeZrO2 catalyst

    OpenAIRE

    Noronha, Fábio Bellot

    2008-01-01

    The catalytic performance of a Pt/CeZrO2 catalyst was tested for ethanol decomposition, steam reforming, partial oxidation, and oxidative steam reforming. At low temperature, the catalyst underwent significant deactivation during ethanol decomposition and steam reforming reactions. Co-feeding oxygen decreased the deactivation rate of the catalyst but adversely affected the selectivity to hydrogen.

  6. SPONTANEOUS CATALYTIC WET AIR OXIDATION DURING PRE-TREATMENT OF HIGH-LEVEL RADIOACTIVE WASTE SLUDGE

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, D.; Herman, C.; Pareizs, J.; Bannochie, C.; Best, D.; Bibler, N.; Fellinger, T.

    2009-10-01

    Savannah River Remediation, LLC (SRR) operates the Defense Waste Processing Facility for the U.S. Department of Energy at the Savannah River Site. This facility immobilizes high-level radioactive waste through vitrification following chemical pretreatment. Catalytic destruction of formate and oxalate ions to carbon dioxide has been observed during qualification testing of non-radioactive analog systems. Carbon dioxide production greatly exceeded hydrogen production, indicating the occurrence of a process other than the catalytic decomposition of formic acid. Statistical modeling was used to relate the new reaction chemistry to partial catalytic wet air oxidation of both formate and oxalate ions driven by the low concentrations of palladium, rhodium, and/or ruthenium in the waste. Variations in process conditions led to increases or decreases in the total oxidative destruction, as well as partially shifting the preferred species undergoing destruction from oxalate ion to formate ion.

  7. Structural, electrical and catalytic properties of ion-implanted oxides

    NARCIS (Netherlands)

    van Hassel, B.A.; Burggraaf, A.J.

    1989-01-01

    The potential application of ion implantation to modify the surfaces of ceramic materials is discussed. Changes in the chemical composition and microstructure result in important variations of the electrical and catalytic properties of oxides.

  8. Partial oxidation of methane over bimetallic copper- and nickel-actinide oxides (Th, U)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Ana C.; Goncalves, A.P.; Gasche, T. Almeida [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal); Ferraria, A.M.; Rego, A.M. Botelho do [Universidade Tecnica de Lisboa, IST, Centro de Quimica-Fisica Molecular and IN, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, M.R.; Bola, A. Margarida [I3N-Universidade de Aveiro, Department Fisica, Aveiro (Portugal); Branco, J.B., E-mail: jbranco@itn.p [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Estrada Nacional 10, 2686-953 Sacavem (Portugal)

    2010-05-14

    The study of partial oxidation of methane (POM) over bimetallic nickel- or copper-actinide oxides was undertaken. Binary intermetallic compounds of the type AnNi{sub 2} (An = Th, U) and ThCu{sub 2} were used as precursors and the products (2NiO.UO{sub 3}, 2NiO.ThO{sub 2} and 2CuO.ThO{sub 2}) characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and temperature-programmed reduction. The catalysts were active and selective for the conversion of methane to H{sub 2} and CO and stable for a period of time of {approx}18 h on stream. The nickel catalysts were more active and selective than the copper catalyst and, under the same conditions, show a catalytic behaviour comparable to that of a platinum commercial catalyst, 5 wt% Pt/Al{sub 2}O{sub 3}. The catalytic activity increases when uranium replaces thorium and the selectivity of this type of materials is clearly different from that of single metal oxides and/or mechanical mixtures. The good catalytic behaviour of the bimetallic copper- and nickel-actinide oxides was attributed to an unusual interaction between copper or nickel oxide and the actinide oxide phase as showed by H{sub 2}-TPR, XPS and Raman analysis of the catalysts before and after reaction.

  9. Catalytic Oxidation of Allylic Alcohols to Methyl Esters

    DEFF Research Database (Denmark)

    Gallas-Hulin, Agata; Kotni, Rama Krishna; Nielsen, Martin

    2017-01-01

    Aerobic oxidation of allylic alcohols to methyl esters using gold nanoparticles supported on different metal oxide carriers has been performed successfully under mild conditions (room temperature, 0.1 MPa O2) without significant loss of catalytic activity. The effects of different reaction...... parameters are studied to find the suitable reaction conditions. All catalysts are characterised by XRD, XRF and TEM. Among these catalysts, Au/TiO2 showed the most efficient catalytic activity towards the selective oxidation of allylic alcohols to the corresponding esters. Moreover, the same Au/TiO2...... to synthesize methyl esters from allylic alcohols....

  10. Catalytic abatement of nitrous oxide from nitric and production

    NARCIS (Netherlands)

    Oonk, J.

    1998-01-01

    Nitric acid production is identified as a main source of nitrous oxide. Options for emission reduction however are not available. TNO and Hydro Agri studied the technological and economic feasibility of catalytic decomposition of nitrous oxide in nitric acid tail-gases. Although in literature

  11. Catalytic wet peroxide oxidation of formic acid in wastewater with ...

    African Journals Online (AJOL)

    2016-07-03

    Jul 3, 2016 ... ABSTRACT. The catalytic wet oxidation of formic acid, using hydrogen peroxide as the oxidizing agent over naturally-occurring iron ore, was explored. Firstly, the decomposition of hydrogen peroxide to its hydroxyl radicals (HO• and HOO•) over naturally-occurring iron ore was investigated. The reaction was ...

  12. Catalytic wet peroxide oxidation of formic acid in wastewater with ...

    African Journals Online (AJOL)

    The catalytic wet oxidation of formic acid, using hydrogen peroxide as the oxidizing agent over naturally-occurring iron ore, was explored. Firstly, the decomposition of hydrogen peroxide to its hydroxyl radicals (HO• and HOO•) over naturally-occurring iron ore was investigated. The reaction was monitored by ATR FTIR by ...

  13. Catalytic oxidative cracking of hexane as a route to olefins

    NARCIS (Netherlands)

    Boyadjian, C.A.; Lefferts, Leonardus; Seshan, Kulathuiyer

    2010-01-01

    Catalytic oxidative cracking of naphtha is conceptually an alternative process to steam cracking. The performance of sol–gel synthesized Li/MgO in oxidative cracking of hexane as a model compound of naphtha, has been studied and compared to that of conventionally prepared catalyst. At a temperature

  14. CATALYTIC HYDROGENATION AND OXIDATION OF BIOMASS-DERIVED LEVULINIC ACID

    OpenAIRE

    Yan Gong; Lu Lin; Zhipei Yan

    2011-01-01

    Levulinic acid (LA), 4-oxo-pentanoic acid, is a new platform chemical with various potential uses. In this paper, catalytic hydrogenation and oxidation of levulinic acid were studied. It was shown from experiments that levulinic acid can be hydrogenated to γ-valerolactone (GVL) over transition metal catalysts and oxidative-decarboxylated to 2-butanone (methyl-ethyl-ketone, MEK) and methyl-vinyl-ketone (MVK) by cupric oxide (CuO), cupric oxide/cerium oxide (CuO/CeO2), cupric oxide/ alumina (Cu...

  15. Synthesis and characterization of formaldehyde by catalytic oxidation of methanol

    International Nuclear Information System (INIS)

    Salman, M.; Answer, J.; Zaman, W.U.

    2008-01-01

    The catalytic oxidation of methanol to formaldehyde is studied over copper and silver catalysts. The impact of various factors catalytic poisoning, temperature, contact time on the formaldehyde yield have been investigated. An assembly using copper and silver as catalysts has been proposed to prepare formaldehyde in perspective of Pakistan in local industry. All the conditions to optimize the formaldehyde yield were also investigated. The formaldehyde produced was standardized chemically as well as spectroscopically. (author)

  16. Steps to detect catalytic ethylene oxide formation on single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Boecklein, Sebastian; Guenther, Sebastian; Reichelt, Robert; Seibald, Markus; Preimesser, Andreas; Ehrensberger, Martin; Rozsa, Gergely; Wintterlin, Joost [Ludwig-Maximilians-Universitaet, 81377 Muenchen (Germany)

    2010-07-01

    As part of a project to bridge the ''pressure gap'' for the catalytic synthesis of ethylene oxide (EtO) on Ag surfaces we have undertaken extensive studies in a model reactor. The investigations aimed at finding conditions under which the production of EtO can be unambiguously and quantitatively detected on single crystal Ag surfaces, a challenging task because of the extremely low ethylene-to-EtO reaction probability. The experiments were performed in a specially designed reactor, and they involved the variation of partial pressures, temperature, and type of Ag samples (powders and polycrystalline sheets), and great effort was expended for proper background subtraction. We find that for the sheets an essential ingredient is an activation treatment by annealing in oxygen, which raises the activity by more than one order of magnitude. There are indications that subsurface O atoms are created by this pretreatment. The maximum values obtained for activity, selectivity, yield, and reaction probability allow us to predict that EtO produced on a single Ag crystal can indeed be detected under flow conditions in a UHV chamber. Experiments on the deactivation show that sintering plays an important role for the dispersed samples, but that there is an additional deactivation process for the sheets that is not caused by sintering or poisoning.

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

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

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

  18. Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

    Directory of Open Access Journals (Sweden)

    Carmen Moreno-Marrodan

    2017-04-01

    Full Text Available The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible.

  19. Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes

    Science.gov (United States)

    Moreno-Marrodan, Carmen; Liguori, Francesca

    2017-01-01

    The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design. A comparison with batch and industrial processes is provided whenever possible. PMID:28503209

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

    Indian Academy of Sciences (India)

    tion in the development of catalysis, magnetism, molec- ular architectures and materials chemistry. Oxidation of alcohols to carbonyl compounds is one of the most pivotal functional group transformations in organic synthesis. Three important natural enzymes used for oxidation reactions are cytochrome P-450, per- oxidases ...

  1. Bactericidal activity of partially oxidized nanodiamonds.

    Science.gov (United States)

    Wehling, Julia; Dringen, Ralf; Zare, Richard N; Maas, Michael; Rezwan, Kurosch

    2014-06-24

    Nanodiamonds are a class of carbon-based nanoparticles that are rapidly gaining attention, particularly for biomedical applications, i.e., as drug carriers, for bioimaging, or as implant coatings. Nanodiamonds have generally been considered biocompatible with a broad variety of eukaryotic cells. We show that, depending on their surface composition, nanodiamonds kill Gram-positive and -negative bacteria rapidly and efficiently. We investigated six different types of nanodiamonds exhibiting diverse oxygen-containing surface groups that were created using standard pretreatment methods for forming nanodiamond dispersions. Our experiments suggest that the antibacterial activity of nanodiamond is linked to the presence of partially oxidized and negatively charged surfaces, specifically those containing acid anhydride groups. Furthermore, proteins were found to control the bactericidal properties of nanodiamonds by covering these surface groups, which explains the previously reported biocompatibility of nanodiamonds. Our findings describe the discovery of an exciting property of partially oxidized nanodiamonds as a potent antibacterial agent.

  2. A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

    Science.gov (United States)

    Conte, Marco; Wilson, Karen; Chechik, Victor

    2010-10-01

    A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.

  3. An Overview of Recent Advances of the Catalytic Selective Oxidation of Ethane to Oxygenates

    Directory of Open Access Journals (Sweden)

    Robert D. Armstrong

    2016-05-01

    Full Text Available The selective partial oxidation of short chain alkanes is a key challenge within catalysis research. Direct ethane oxidation to oxygenates is a difficult aim, but potentially rewarding, and it could lead to a paradigm shift in the supply chain of several bulk chemicals. Unfortunately, low C–H bond reactivity and kinetically labile products are just some reasons affecting the development and commercialisation of such processes. Research into direct ethane oxidation is therefore disparate, with approaches ranging from oxidation in the gas phase at high temperatures to enzyme catalysed hydroxylation under ambient conditions. Furthermore, in overcoming the barrier posed by the chemically inert C–H bond a range of oxidants have been utilised. Despite years of research, this remains an intriguing topic from both academic and commercial perspectives. Herein we describe some recent developments within the field of catalytic ethane oxidation focusing on the formation of oxygenated products, whilst addressing the key challenges which are still to be overcome.

  4. 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 ...

  5. Solid Waste Decontamination by Thermal Desorption and Catalytic Oxidation Methods

    Czech Academy of Sciences Publication Activity Database

    Šolcová, Olga; Topka, Pavel; Soukup, Karel; Jirátová, Květa; Váňová, H.; Kaštánek, František

    2014-01-01

    Roč. 68, č. 9 (2014), s. 1279-1282 ISSN 0366-6352 R&D Projects: GA MPO FR-TI1/059 Institutional support: RVO:67985858 Keywords : thermal desorption * catalytic oxidation * soil decontamination Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.468, year: 2014

  6. Catalytic dehydrogenation of light alkanes on metals and metal oxides

    NARCIS (Netherlands)

    Sattler, Jesper J H B|info:eu-repo/dai/nl/328235601; Ruiz-Martinez, Javier|info:eu-repo/dai/nl/341386405; Santillan-Jimenez, Eduardo|info:eu-repo/dai/nl/323171958; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397

    2014-01-01

    A study is conducted to demonstrate catalytic dehydrogenation of light alkanes on metals and metal oxides. The study provides a complete overview of the materials used to catalyze this reaction, as dehydrogenation for the production of light olefins has become extremely relevant. Relevant factors,

  7. Trends in the Catalytic CO Oxidation Activity of Nanoparticles

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Falsig, Hanne; Larsen, Britt Hvolbæk

    2008-01-01

    Going for gold: Density functional calculations show how gold nanoparticles are more active catalysts for CO oxidation than other metal nanoparticles. The high catalytic activity of nanosized gold clusters at low temperature is found to be related to the ability of low-coordinate metal atoms...

  8. Structure and catalytic reactivity of Rh oxides

    DEFF Research Database (Denmark)

    Gustafson, J.; Westerström, R.; Resta, A.

    2009-01-01

    Using a combination of experimental and theoretical techniques, we show that a thin RhO2 surface oxide film forms prior to the bulk Rh2O3 corundum oxide on all close-packed single crystal Rh surfaces. Based on previous reports, we argue that the RhO2 surface oxide also forms on vicinal Rh surfaces...... as well as on Rh nanoparticles. The detailed structure of this film was previously determined using UHV based techniques and density functional theory. In the present paper, we also examine the structure of the bulk Rh2O3 corundum oxide using surface X-ray diffraction. Being armed with this structural...... information, we have explored the CO oxidation reaction over Rh(1 1 1), Rh(1 0 0) and Pt25Rh75(1 0 0) at realistic pressures using in situ surface X-ray diffraction and online mass spectrometry. In all three cases we find that an increase of the CO2 production coincides with the formation of the thin RhO2...

  9. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pozan, Gulin Selda, E-mail: gpozan@istanbul.edu.tr [Istanbul University, Faculty of Engineering, Chemical Engineering Department, Avcilar 34320, Istanbul (Turkey)

    2012-06-30

    Highlights: Black-Right-Pointing-Pointer {alpha}-Al{sub 2}O{sub 3}, obtained from Bohmite, as a support for enhancing of the activity. Black-Right-Pointing-Pointer The support material for catalytic oxidation. Black-Right-Pointing-Pointer 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{sub 2} modified with different supports. {alpha}-Al{sub 2}O{sub 3} and {gamma}-Al{sub 2}O{sub 3} obtained from Boehmite, {gamma}-Al{sub 2}O{sub 3} (commercial), SiO{sub 2}, TiO{sub 2} and ZrO{sub 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{sub 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{sub 2}/{alpha}-Al{sub 2}O{sub 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 Degree-Sign 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.

  10. 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.

  11. Direct partial oxidation of methane via single-site chemistry

    Science.gov (United States)

    Kakekhani, Arvin; Norskov, Jens

    Methane (CH4), the cheapest source of hydrocarbons, is a difficult-to-store and hard-to-convert chemical, due to strong and isotropic C-H bonds. Having a selective and efficient method to partially oxidize methane into more useful chemicals including methanol, formaldehyde and alkenes has long been an open challenge for catalysis community. The main challenge is selectivity: if a catalytic material interacts strongly with methane, sufficient to break one C-H bond, it breaks all other bonds of the derivative molecules, as well. This leads to over-oxidization to CO2. Here using density functional theory (DFT) modelings, we discuss the possibility of using defective (vacancy rich) 2-d materials e.g., MoS2 to effectively trap single transition metal atoms; thereby, creating a single-site chemistry to enhance the selectivity of methane oxidation process. A single-site chemistry leads to competition between intermediates and products for limited active sites. Our strategy is to use this as an effective means to block unwanted reaction pathways leading to over-oxidization. United States department of energy.

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

    Indian Academy of Sciences (India)

    Oxidation of alcohols to carbonyl compounds is one of the most pivotal functional group transformations in organic synthesis. Three important natural enzymes ..... 6. Benzyl alcohol. Benzaldehyde. 57. 1-Phenylethanol. Acetophenone. 65. Cyclohexanol. Cyclohexanone. 49 a Reaction time, 5 h. b Yields based on substrate.

  13. Catalytic oxidation for treatment of ECLSS and PMMS waste streams

    Science.gov (United States)

    Akse, James R.; Jolly, Clifford D.

    1991-01-01

    It is shown that catalytic oxidation is an effective technique for the removal of trace organic contaminants in a multifiltration potable processor's effluent. Essential elements of this technology are devices that deliver oxygen to the influent, and remove gaseous reaction byproducts from the effluent, via hollow-tube, gas-permeable membranes. Iodine, which poisons existing catalysis, is removed by a small deiodination bed prior to catalytic reactor entrance. The catalyst used is a mixture of Pt and Ru deposited on carbon, operating at 125-160 C and 39-90 psi pressures.

  14. Novel synthesis and shape-dependent catalytic performance of Cu-Mn oxides for CO oxidation

    Science.gov (United States)

    Li, Zhixun; Wang, Honglei; Wu, Xingxing; Ye, Qinglan; Xu, Xuetang; Li, Bin; Wang, Fan

    2017-05-01

    Transition metal oxides with large specific surface area are attractive for high-activity catalysts, and hierarchical structures of transition metal oxides with porous feature possess the structural advantage in the transfer of gaseous reactant and product. In this work, porous Cu-Mn oxides with high surface area were successfully obtained through low-temperature coprecipitation method in alcohol/water solvent and then post-annealing. The addition of alcohol showed great influences on the shape and catalytic performances for CO oxidation. Dumbbell-like Cu-Mn oxide particles with splitting ends displayed high catalytic activity and a complete conversion of CO was achieved at 45 °C, suggesting a shape-dependent catalytic activity. The oxidative activity was attributed to a combination of factors including specific surface area, active surface oxygen species and Mn(IV) cations. The results may supply a new thought to design high-performance Cu-Mn oxide catalysts.

  15. Visualizing the mobility of silver during catalytic soot oxidation

    DEFF Research Database (Denmark)

    Gardini, Diego; Christensen, Jakob M.; Damsgaard, Christian Danvad

    2016-01-01

    The catalytic activity and mobility of silver nanoparticles used as catalysts in temperature programmed oxidation of soot:silver (1:5 wt:wt) mixtures have been investigated by means of flow reactor experiments and in situ environmental transmission electron microscopy (ETEM). The carbon oxidation...... temperature was significantly lower compared to uncatalyzed soot oxidation with soot and silver loosely stirred together (loose contact) and lowered further with the two components crushed together (tight contact). The in situ TEM investigations revealed that the silver particles exhibited significant...

  16. Selective catalytic oxidations of alkylaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, R.W. [Celanese GmbH, Oberhausen (Germany); Roehrscheid, F. [Hoechst AG, Frankfurt am Main (Germany). Zentralforschung und Technologie

    1998-12-31

    Focused to the guidelines of `Sustainable Development` `Responsible Care` and `Customer Satisfaction`, modern production processes are critically assessed on their balance between their ecological benefits and their economical parameters as well as their value to the community. Also in the area of fine chemicals, it is obvious that more and more processes are devolved which save feedstock, reduce emissions and minimize the potential for safety hazards: Less additive but more integrated protection of the environment yielding ecologically highly valuable processes. The described production of aromatic carboxylic acids is an ideal example for such a modern process. Nowadays the synthesis of derivatives of benzoic acid utilizes air as Ideal oxidant and acetic acid as environmental unquestionable solvent. The major byproduct of the oxidation reaction is water in some cases, dependend on the substrate also carbon dioxide. (orig.)

  17. Method For Selective Catalytic Reduction Of Nitrogen Oxides

    Science.gov (United States)

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

  18. Investigation of the Origin of Catalytic Activity in Oxide-Supported Nanoparticle Gold

    Energy Technology Data Exchange (ETDEWEB)

    Harrison, Ian [Univ. of Virginia, Charlottesville, VA (United States)

    2017-05-26

    Since Haruta’s discovery in 1987 of the surprising catalytic activity of supported Au nanoparticles, we have seen a very large number of experimental and theoretical efforts to explain this activity and to fully understand the nature of the behavior of the responsible active sites. In 2011, we discovered that a dual catalytic site at the perimeter of ~3nm diameter Au particles supported on TiO2 is responsible for oxidative catalytic activity. O2 molecules bind with Au atoms and Ti4+ ions in the TiO2 support and the weakened O-O bond dissociates at low temperatures, proceeding to produce O atoms which act as oxidizing agents for the test molecule, CO. The papers supported by DOE have built on this finding and have been concerned with two aspects of the behavior of Au/TiO2 catalysts: (1). Mechanistic behavior of dual catalytic sites in the oxidation of organic molecules such as ethylene and acetic acid; (2). Studies of the electronic properties of the TiO2 (110) single crystal in relation to its participation in charge transfer at the occupied dual catalytic site. A total of 20 papers have been produced through DOE support of this work. The papers combine IR spectroscopic investigations of Au/TiO2 catalysts with surface science on the TiO2(110) and TiO2 nanoparticle surfaces with modern density functional modeling. The primary goals of the work were to investigate the behavior of the dual Au/Ti4+ site for the partial oxidation of alcohols to acids, the hydrogenation of aldehydes and ketones to alcohols, and the condensation of oxygenate intermediates- all processes related to the utilization of biomass in the production of useful chemical energy sources.

  19. Solid State, Surface and Catalytic Studies of Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Kung, H. H.

    2004-11-23

    This project investigates the catalytic properties of oxides for the selective oxidative dehydrogenation of light alkanes and for hydrocarbon reduction of NO{sub x}. Various vanadium oxide based catalysts were investigated to elucidate the relationship between the chemical and structural properties of the catalysts and their selectivity for the formation of alkenes. It was found that vanadium oxide units that are less reducible give higher selectivities. For hydrocarbon reduction of NO{sub x}, it was found that alumina-based catalysts can be effective at higher temperatures than the corresponding zeolite-based catalysts. On some catalysts, such as SnO{sub 2}/Al{sub 2}O{sub 3}. Ag/Al{sub 2}O{sub 3}, the alumina participates directly in the reaction, making the catalyst bifunctional. These results are useful in research to improve the performance of this stress of catalysts.

  20. Catalytic oxidation of volatile organic compounds (VOCs) - A review

    Science.gov (United States)

    Kamal, Muhammad Shahzad; Razzak, Shaikh A.; Hossain, Mohammad M.

    2016-09-01

    Emission of volatile organic compounds (VOCs) is one of the major contributors to air pollution. The main sources of VOCs are petroleum refineries, fuel combustions, chemical industries, decomposition in the biosphere and biomass, pharmaceutical plants, automobile industries, textile manufacturers, solvents processes, cleaning products, printing presses, insulating materials, office supplies, printers etc. The most common VOCs are halogenated compounds, aldehydes, alcohols, ketones, aromatic compounds, and ethers. High concentrations of these VOCs can cause irritations, nausea, dizziness, and headaches. Some VOCs are also carcinogenic for both humans and animals. Therefore, it is crucial to minimize the emission of VOCs. Among the available technologies, the catalytic oxidation of VOCs is the most popular because of its versatility of handling a range of organic emissions under mild operating conditions. Due to that fact, there are numerous research initiatives focused on developing advanced technologies for the catalytic destruction of VOCs. This review discusses recent developments in catalytic systems for the destruction of VOCs. Review also describes various VOCs and their sources of emission, mechanisms of catalytic destruction, the causes of catalyst deactivation, and catalyst regeneration methods.

  1. Catalytic Activity of Oxidized Carbon Black and Graphene Oxide for the Crosslinking of Epoxy Resins

    Directory of Open Access Journals (Sweden)

    Maria Rosaria Acocella

    2017-04-01

    Full Text Available This article compares the catalytic activities of oxidized carbon black (oCB and graphene oxide (eGO samples on the kinetics of a reaction of diglycidyl ether of bisphenol A (DGEBA with a diamine, leading to crosslinked insoluble networks. The study is mainly conducted by rheometry and Differential Scanning Calorimetry (DSC. Following the same oxidation procedure, CB samples are more efficiently oxidized than graphite samples. For instance, CB and graphite samples with high specific surface areas (151 and 308 m2/g, as oxidized by the Hummers’ method, exhibit O/C wt/wt ratios of 0.91 and 0.62, respectively. Due to the higher oxidation levels, these oCB samples exhibit a higher catalytic activity toward the curing of epoxy resins than fully exfoliated graphene oxide.

  2. Catalytic oxidation of carbon monoxide over supported palladium nanoparticles

    Science.gov (United States)

    Soni, Keshav Chand; Krishna, R.; Chandra Shekar, S.; Singh, Beer

    2016-01-01

    Catalytic oxidation of CO with ozone had been studied over Al2O3 and SiO2 supported Pd nanoparticles which was synthesized by two different methods. The polyol method mainly resulted in highly dispersed Pd particles on the support, while the impregnation method resulted in agglomeration Pd particles on the support. Supported Pd nanoparticles synthesized from PdCl2 in the presence of poly ( N-vinylpyrrolidone) (PVP) by chemical reduction. The catalysts were characterized by X-ray diffraction, N2 BET surface area, pore size distributions, CO chemisorption, TEM and H2-temperature programmed reduction. The physico-chemical properties were well correlated with activity data. Characterizations of XRD and TEM show that the surface Pd nanoparticles are highly dispersed over Al2O3 and SiO2. The catalytic activity was dependent upon ozone/CO ratio, contact times, and the reaction temperature. The extent of carbon monoxide oxidation was proportional to the catalytically ozone decomposition. The PVP synthesized Pd/A2O3 catalyst had been found to be highly active for complete CO removal at room temperature. The higher activity of the nanocatalyst was attributed to small particle size and higher dispersion of Pd over support.

  3. Catalytic oxidative desulfurization of liquid hydrocarbon fuels using air

    Science.gov (United States)

    Sundararaman, Ramanathan

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

  4. Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

    2014-07-15

    Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

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

    Science.gov (United States)

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

    1987-01-01

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

  6. 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.

  7. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi

    2014-03-01

    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  8. Catalytic oxidation. VI. Oxidation of labeled olefins over silver

    International Nuclear Information System (INIS)

    Cant, N.W.; Hall, W.K.

    1978-01-01

    The oxidation of ethylene and propylene labeled with deuterium in various positions and the cooxidation of unlabeled olefins with the corresponding 14 C-labeled epoxides have been studied over a silver catalyst. The latter measurements showed that, in both systems at 200 to 220 0 C, a portion of the CO 2 was produced by destruction of the product epoxide, but that the oxygen exchange between olefin and epoxide was nil. Oxidation of either cis- or trans-ethylene-d 2 yielded a mixture of the cis- and trans-d 2 epoxides which was about 92% equilibrated. Relative rate measurements showed that substitution of deuterium for hydrogen in ethylene increased the yield of epoxide substantially. Such kinetic isotope effects were even more pronounced with propylene for which the oxidation of CD 3 CHCH 2 and CD 3 CDCD 2 gave a 10 to 14% selectivity to the corresponding epoxides compared with 2 to 5% for CH 3 CHCH 2 , CH 3 CDCH 2 , and CH 3 CHCD 2 . The kinetic isotope effects can be qualitatively explained in terms of a normal primary effect in the further oxidation of an intermediate which is common to both epoxide formation and total oxidation. The significance of these findings to previous suggestions regarding surface intermediates and the mechanism of these oxidations is discussed. 4 figures, 5 tables

  9. Catalytic aerobic oxidation of bio-renewable chemicals

    DEFF Research Database (Denmark)

    Gorbanev, Yury

    , EDS, XRF and other methods. Supported gold and ruthenium hydroxide catalyst systems were explored for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDA), a potential polymer building block for the plastic industry, or its dimethyl ester (FDMC). High product...... selectivities and yields were obtained under optimized conditions. Heterogeneous catalysts consisting of Au nanoparticles on different supports were shown to efficiently oxidize HMF to FDA or FDMC in water or methanol, respectively. Additionally, the reaction conditions were shown to be adjustable...... with supported Ru(OH)x catalysts in organic solvents. The examined catalyst systems and reaction conditions were also shown to be applicable for the efficient oxidation of other substituted furans. Furthermore, novel catalytic systems comprising vanadia supported on zeolites were investigated for the aerobic...

  10. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  11. Electro-catalytic oxidation of reactive Orange 107 using cerium doped oxides of Nd3+ nanoparticle

    International Nuclear Information System (INIS)

    Rajkumar, K.; Muthukumar, M.; Mangalaraja, R.V.

    2011-01-01

    A new rare earth doped cerium oxide powder was used as a catalyst to investigate the removal of colour and TOC from simulated wastewater of Reactive Orange 107. The electro oxidation process was carried out in the reactor in presence of an electrolyte NaCl. Graphite electrode was used as anode and cathode and electrolysis were carried out at a current density of 34.96 mAcm -2 with a catalyst concentration of 0.05g L -1 . In order to find the efficiency of nanocatalyst, experiments were also conducted without catalyst. From the experiment, it was found that complete colour removal was achieved on electrocatalytic oxidation as well as electro oxidation. When comparing the above processes, catalytic oxidation shows more efficient than electro oxidation. With respect to the degradation of the dye, catalytic oxidation shows more TOC removal than the oxidation taken place without catalyst. It infers that even though the electro-catalytic oxidation process achieves complete decolouration but it does not achieve complete mineralisation. The FTIR and GCMS studies confirmed the formation of by-products. (author)

  12. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    Science.gov (United States)

    You, Fu-Tian; Yu, Guang-Wei; Wang, Yin; Xing, Zhen-Jiao; Liu, Xue-Jiao; Li, Jie

    2017-08-01

    Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnOx)-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnOx and the test conditions on the reaction. MLAC with 7.5 wt.% MnOx (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O2, room temperature and GHSV ca. 16000 h-1. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O2 concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnOx loading is assumed to be related to Mn4+/Mn3+ ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnOx lattice O transfer is proposed.

  13. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  14. 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.

  15. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    KAUST Repository

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  16. Partial Oxidation of Methane Over Co-ZSM-5: Tuning the Oxygenate Selectivity by Altering the Preparation Route

    NARCIS (Netherlands)

    Beznis, N.|info:eu-repo/dai/nl/304837296; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Bitter, J.H.|info:eu-repo/dai/nl/160581435

    2013-01-01

    For the first time the possibility to partially oxidize methane to methanol and formaldehyde at low temperature over Co-ZSM-5 using air is shown. The influence of the preparation method on the nature of the cobalt species is investigated. In addition, the catalytic activity and selectivity for

  17. The catalytic activity of several tungsten oxides for the oxidation of propene

    International Nuclear Information System (INIS)

    De Rossi, S.; Schiavello, M.; Rome Univ.; Iguchi, E.; Tilley, R.J.D.

    1976-01-01

    A study has been made of the catalytic oxidation of propene over the oxides WO 3 , WOsub(2,95), WOsub(2,90), WOsub(2,72) and Wo 2 , which were selected because they possess specific features of chemical and structural interest rather than for their catalytic ability. It was found that the oxides WOsub(2,95), WOsub(2,90) and WOsub(2,72) all selectively produce acrolein in small amounts. The oxides WO 3 and WO 2 were non-selective and rather inactive. The results are discussed in terms of a mechanism involving both variable valence in the crystal and the specific structural geometry of these compounds. (orig.) [de

  18. Catalytic degradation of brominated flame retardants by copper oxide nanoparticles.

    Science.gov (United States)

    Yecheskel, Yinon; Dror, Ishai; Berkowitz, Brian

    2013-09-01

    The catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) was investigated. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis were also compared to Fenton oxidation and nano zero-valent iron (nZVI) reduction methods. BFRs have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use and become contaminants. The two studied BFRs were fully degraded with sufficient time (hours to days) and oxidation agent (H2O2). Shorter reaction times showed differences in reaction pathway and kinetics. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24h, while the TBNPA was degraded by 85% within 12h. Electron Spin Resonance (ESR) measurements show generation of both hydroxyl and superoxide radicals. In addition, inhibition of 2,4-DBP degradation in the presence of spin traps implies a radical degradation mechanism. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. VUV photo-oxidation of gaseous benzene combined with ozone-assisted catalytic oxidation: Effect on transition metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Haibao, E-mail: seabao8@gmail.com [School of Environmental Science and Engineering, Sun Yat-Sen University (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology (Sun Yat-sen University) (China); Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo [School of Environmental Science and Engineering, Sun Yat-Sen University (China)

    2017-01-01

    Graphical abstract: Mn nanoparticles are highly dispersed on ZSM-5 and most efficient in benzene degradation in the VUV-OZCO process. - Highlights: • Vacuum UV irradiation is well combined with O{sub 3} catalytic oxidation. • O{sub 3} byproducts was used to enhance catalytic oxidation of VOCs. • Mn/ZSM-5 achieved the best catalytic activity for benzene degradation. - Abstract: Volatile organic compounds (VOCs) cause the major air pollution concern. In this study, a series of ZSM-5 supported transition metals were prepared by impregnation method. They were combined with vacuum UV (VUV) photo-oxidation in a continuous-flow packed-bed reactor and used for the degradation of benzene, a typical toxic VOCs. Compared with VUV photo-oxidation alone, the introduction of catalysts can greatly enhance benzene oxidation under the help of O{sub 3}, the by-products from VUV irradiation, via ozone-assisted catalytic oxidation (OZCO). The catalytic activity of transition metals towards benzene oxidation followed the order: Mn > Co > Cu > Ni > Fe. Mn achieved the best catalytic activity due to the strongest capability for O{sub 3} catalytic decomposition and utilization. Benzene and O{sub 3} removal efficiency reached as high as 97% and 100% after 360 min, respectively. O{sub 3} was catalytically decomposed, generating highly reactive oxidants such as ·OH and ·O for benzene oxidation.

  20. Catalytic Partial Oxidation Reforming of JP8 AND S8

    National Research Council Canada - National Science Library

    Howell, Thomas G

    2007-01-01

    .... fuel processing prototype utilizing military logistic fuels JP8 and S8. S8 is a sulfur-free Fisher-Tropsch fuel, while JP8 is a multi-fuel blend, which could impact reforming efficiency, product distribution and byproduct production...

  1. Catalytic Partial Oxidation Reforming of JP8 AND S8

    Science.gov (United States)

    2007-06-01

    Heats of Combustion for fuels and reformate..................................................... 44 Table 5: Design points for Aspen reformer with...value for CO. By reforming JP8 to produce hydrogen , fuels burn more efficiently and emissions are reduced. The current internal combustion engines are...in production of hydrogen as well as a decrease in the amount of heat used in the steam reforming. 19 III. Methodology Aspen Fuel Processor

  2. Solvent-free Oxidation of Alcohols and Mild Catalytic Deprotection of ...

    African Journals Online (AJOL)

    tetrabromobenzene- 1,3-disulphonamide (TBBDA) can be used for solvent-free oxidation of primary and secondary alcohols to the corresponding carbonyl compounds without over-oxidation, and efficient catalytic deprotection of various silyl ...

  3. Solvent-free Oxidation of Alcohols and Mild Catalytic Deprotection of ...

    African Journals Online (AJOL)

    NJD

    tetrabromobenzene-1,3-disulphonamide. (TBBDA) can be used for solvent-free oxidation of primary and secondary alcohols to the corresponding carbonyl compounds without over-oxidation, and efficient catalytic deprotection of various silyl ...

  4. Catalytic properties and biomedical applications of cerium oxide nanoparticles

    KAUST Repository

    Walkey, Carl D.

    2014-11-10

    Cerium oxide nanoparticles (nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of nanoceria in animal studies? 2) What are the considerations to develop nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials?

  5. Catalytic hydrogen peroxide decomposition La1-xSrxCoO3-δ perovskite oxides

    NARCIS (Netherlands)

    Dam, T.V.A.; Olthuis, Wouter; Bergveld, Piet; van den Berg, Albert

    2005-01-01

    Lanthanide perovskite oxides are mentioned as material for hydrogen peroxide sensor because they can catalytically decompose hydrogen peroxide in an aqueous medium. The catalytic properties of these perovskite oxides to hydrogen peroxide are suggested due to their oxygen vacancies influenced by the

  6. Nanorods of manganese oxides: Synthesis, characterization and catalytic application

    Science.gov (United States)

    Yang, Zeheng; Zhang, Yuancheng; Zhang, Weixin; Wang, Xue; Qian, Yitai; Wen, Xiaogang; Yang, Shihe

    2006-03-01

    Single-crystalline nanorods of β-MnO 2, α-Mn 2O 3 and Mn 3O 4 were successfully synthesized via the heat-treatment of γ-MnOOH nanorods, which were prepared through a hydrothermal method in advance. The calcination process of γ-MnOOH nanorods was studied with the help of Thermogravimetric analysis and X-ray powder diffraction. When the calcinations were conducted in air from 250 to 1050 °C, the precursor γ-MnOOH was first changed to β-MnO 2, then to α-Mn 2O 3 and finally to Mn 3O 4. When calcined in N 2 atmosphere, γ-MnOOH was directly converted into Mn 3O 4 at as low as 500 °C. Transmission electron microscopy (TEM) and high-resolution TEM were also used to characterize the products. The obtained manganese oxides maintain the one-dimensional morphology similar to the precursor γ-MnOOH nanorods. Further experiments show that the as-prepared manganese oxide nanorods have catalytic effect on the oxidation and decomposition of the methylene blue (MB) dye with H 2O 2.

  7. Methylene Blue Inhibits Caspases by Oxidation of the Catalytic Cysteine.

    Science.gov (United States)

    Pakavathkumar, Prateep; Sharma, Gyanesh; Kaushal, Vikas; Foveau, Bénédicte; LeBlanc, Andrea C

    2015-09-24

    Methylene blue, currently in phase 3 clinical trials against Alzheimer Disease, disaggregates the Tau protein of neurofibrillary tangles by oxidizing specific cysteine residues. Here, we investigated if methylene blue can inhibit caspases via the oxidation of their active site cysteine. Methylene blue, and derivatives, azure A and azure B competitively inhibited recombinant Caspase-6 (Casp6), and inhibited Casp6 activity in transfected human colon carcinoma cells and in serum-deprived primary human neuron cultures. Methylene blue also inhibited recombinant Casp1 and Casp3. Furthermore, methylene blue inhibited Casp3 activity in an acute mouse model of liver toxicity. Mass spectrometry confirmed methylene blue and azure B oxidation of the catalytic Cys163 cysteine of Casp6. Together, these results show a novel inhibitory mechanism of caspases via sulfenation of the active site cysteine. These results indicate that methylene blue or its derivatives could (1) have an additional effect against Alzheimer Disease by inhibiting brain caspase activity, (2) be used as a drug to prevent caspase activation in other conditions, and (3) predispose chronically treated individuals to cancer via the inhibition of caspases.

  8. Mercury Oxidation via Catalytic Barrier Filters Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Wayne Seames; Michael Mann; Darrin Muggli; Jason Hrdlicka; Carol Horabik

    2007-09-30

    In 2004, the Department of Energy National Energy Technology Laboratory awarded the University of North Dakota a Phase II University Coal Research grant to explore the feasibility of using barrier filters coated with a catalyst to oxidize elemental mercury in coal combustion flue gas streams. Oxidized mercury is substantially easier to remove than elemental mercury. If successful, this technique has the potential to substantially reduce mercury control costs for those installations that already utilize baghouse barrier filters for particulate removal. Completed in 2004, Phase I of this project successfully met its objectives of screening and assessing the possible feasibility of using catalyst coated barrier filters for the oxidation of vapor phase elemental mercury in coal combustion generated flue gas streams. Completed in September 2007, Phase II of this project successfully met its three objectives. First, an effective coating method for a catalytic barrier filter was found. Second, the effects of a simulated flue gas on the catalysts in a bench-scale reactor were determined. Finally, the performance of the best catalyst was assessed using real flue gas generated by a 19 kW research combustor firing each of three separate coal types.

  9. Heterogeneous Catalytic Oxidation of Simple Alcohols by Transition Metals.

    Science.gov (United States)

    Jacobse, Leon; Vink, Sebastiaan O; Wijngaarden, Sven; Juurlink, Ludo B F

    2017-09-12

    The "exploding" flask demonstration presents a well-known illustration of heterogeneous catalyzed methanol oxidation. We find that for the same vapor pressure, the demonstration also works for all primary and secondary alcohols up to butanol but not for a tertiary alcohol. Also, we show that the demonstration works for a large range of transition metal catalysts. Hence, this demonstration, which is often applied for the repetitive explosions when methanol is used, may also be used to argue the requirement of initial dehydrogenation of the alcohol to an aldehyde in the catalytic reaction mechanism to support the general insensitivity to reactant molecules in heterogeneous catalysis in contrast to biological catalysis and to provide proof for activity trends as often depicted by volcano plots.

  10. Oxidative catalytic dimerization of methane: Syngas process alternative

    International Nuclear Information System (INIS)

    Salvi, G.

    1991-01-01

    A review of research progress relative to the direct conversion of methane into liquid hydrocarbons through oxidative catalytic dimerization indicates that high carbon (C 2 ) yields can be obtained in experimental conditions in which there is a high linear gas velocity, i.e., velocities greater than 0.45 m/s, at temperatures ranging between 800 and 850 degrees C, and with volumetric methane/oxygen ratios of 2 to 10. The high linear velocities have the function of preventing back-mixing phenomena and consequent product degradation. The suitable integration of dimerization (exothermic) with cracking (endothermic) of ethane to ethylene and higher olefins, as well as, oligomerization of the olefins to liquid hydrocarbons (synthesis fuels) can allow for the development of an very interesting process from both technical and economic points of view, especially for those countries with a mix of abundant natural gas reserves and scarce petroleum resources

  11. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    Science.gov (United States)

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  12. Catalytic oxidation of NO to NO2 on activated carbon

    International Nuclear Information System (INIS)

    Zhancheng Guo; Yusheng Xie

    2001-01-01

    Catalytic oxidation of NO to NO 2 over activated carbons PAN-ACF, pitch-ACF and coconut-AC at room temperature (30 o C) were studied to develop a method based on oxidative removal of NO from flue gases. For a dry gas, under the conditions of a gas space flow rate 1500 h -1 in the presence of oxygen of 2-20% in volume concentration, the activated coconut carbon with a surface area 1200 m 2 /g converted about 81-94% of NO with increasing oxygen concentration, the pitch based activated carbon fiber with a surface area 1000 m 2 /g about 44-75%, and the polyacrylonitrile-based activated carbon fiber with a surface area 1810 m 2 /g about 25-68%. The order of activity of the activated carbons was PAN-ACF c P NO P O2 β (F/W), where β is 0.042, 0.16, 0.31 for the coconut-AC, the pitch-ACF and the PAN-ACF respectively, and k c is 0.94 at 30 o C. (author)

  13. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    Science.gov (United States)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  14. Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

    International Nuclear Information System (INIS)

    Dzhordano, N.; Bart, D.; Madzhori, R.

    1984-01-01

    A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

  15. Catalytic pleat filter bags for combined particulate separation and nitrogen oxides removal from flue gas streams

    International Nuclear Information System (INIS)

    Park, Young Ok; Choi, Ho Kyung

    2010-01-01

    The development of a high temperature catalytically active pleated filter bag with hybrid filter equipment for the combined removal of particles and nitrogen oxides from flue gas streams is presented. A special catalyst load in stainless steel mesh cartridge with a high temperature pleated filter bag followed by optimized catalytic activation was developed to reach the required nitrogen oxides levels and to maintain the higher collection efficiencies. The catalytic properties of the developed high temperature filter bags with hybrid filter equipment were studied and demonstrated in a pilot scale test rig and a demonstration plant using commercial scale of high temperature catalytic pleated filter bags. The performance of the catalytic pleated filter bags were tested under different operating conditions, such as filtration velocity and operating temperature. Moreover, the cleaning efficiency and residual pressure drop of the catalyst loaded cartridges in pleated filter bags were tested. As result of theses studies, the optimum operating conditions for the catalytic pleated filter bags are determined. (author)

  16. Partial Oxidation of n-Pentane over Vanadium Phosphorus Oxide ...

    African Journals Online (AJOL)

    NICOLAAS

    The selective oxidation ofn-pentane to value-added products, maleic anhydride or phthallic anhydride by vanadium phosphorus oxide loaded on hydroxyapatites as catalysts and oxygen as oxidant was investigated. Hydroxyapatite (HAp) and cobalt- hydroxyapatite (Co-HAp) were prepared by the co-precipitation method ...

  17. Effect of NO2 and water on the catalytic oxidation of soot

    DEFF Research Database (Denmark)

    Christensen, Jakob Munkholt; Grunwaldt, Jan-Dierk; Jensen, Anker Degn

    2017-01-01

    The influence of adding NO2 to 10 vol% O2/N2 on non-catalytic soot oxidation and soot oxidation in intimate or loose contact with a catalyst has been investigated. In non-catalytic soot oxidation the oxidation rate is increased significantly at lower temperatures by NO2. For soot oxidation in tig...... exhibited a volcano-curve dependence on the heat of oxygen chemisorption, and among the tested pure metals and oxides Cr2O3 was the most active catalyst. Further improvements were achieved with a FeaCrbOx binary oxide catalyst.......The influence of adding NO2 to 10 vol% O2/N2 on non-catalytic soot oxidation and soot oxidation in intimate or loose contact with a catalyst has been investigated. In non-catalytic soot oxidation the oxidation rate is increased significantly at lower temperatures by NO2. For soot oxidation in tight...... contact with a Co3O4 catalyst a more reactive NO2-containg atmosphere did not change the oxidation profile significantly during temperature programmed oxidation. This is consistent with the expected Mars van Krevelen mechanism, where the rate limiting step is reaction between carbon and lattice oxygen...

  18. Oxidation-resistant acidic resins prepared by partial carbonization as cocatalysts in synthesis of adipic acid.

    Science.gov (United States)

    Wei, Huijuan; Li, Hongbian; Liu, Yangqing; Jin, Peng; Wang, Xiangyu; Li, Baojun

    2012-08-01

    The oxidation-resistant acidic resins are of great importance for the catalytic oxidation systems. In this paper, the oxidatively stable acidic resins are obtained from the cation ion exchange resins (CIERs) through the thermal treatment in N(2) atmosphere. The structure and properties of the thermally treated CIERs were characterized by chemical analysis, Fourier transform infrared (FT-IR) spectra, acid capacity measurement and scanning electron microscope (SEM). The thermally treated CIERs possess high acid capacity up to 4.09 mmol g(-1). A partial carbonization is observed in the thermal treatment process of CIERs, but the morphology of resin spheres maintains well. The as-prepared CIERs are used as solid acids to assist the hydrogen peroxide oxidation of cyclohexene to adipic acid (ADA) with tungstic acid as the catalyst precursor. The improved yields of ADA in the recycling reaction are obtained in the presence of acidic CIERs. Meanwhile, the unproductive decomposition of H(2)O(2) is effectively suppressed. The high yields of ADA (about 81%) are kept by the thermally treated CIERs even after the fifth cycle. The thermally treated CIERs exhibit excellent acid-catalytic performance and possess remarkable oxidation-resistant capability.

  19. Selective oxidation

    International Nuclear Information System (INIS)

    Cortes Henao, Luis F.; Castro F, Carlos A.

    2000-01-01

    It is presented a revision and discussion about the characteristics and factors that relate activity and selectivity in the catalytic and not catalytic partial oxidation of methane and the effect of variables as the temperature, pressure and others in the methane conversion to methanol. It thinks about the zeolites use modified for the catalytic oxidation of natural gas

  20. Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

    International Nuclear Information System (INIS)

    Li Ning; Descorme, Claude; Besson, Michele

    2007-01-01

    A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3 wt.% Ru/ZrO 2 . 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3 wt.% Ru/ZrO 2 is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393 K) and lower total pressure (3 MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  2. Thermal catalytic oxidation of octachloronaphthalene over anatase TiO2 nanomaterial and its hypothesized mechanism

    Science.gov (United States)

    Su, Guijin; Li, Qianqian; Lu, Huijie; Zhang, Lixia; Huang, Linyan; Yan, Li; Zheng, Minghui

    2015-12-01

    As an environmentally-green technology, thermal catalytic oxidation of octachloronaphthalene (CN-75) over anatase TiO2 nanomaterials was investigated at 300 °C. A wide range of oxidation intermediates, which were investigated using various techniques, could be of three types: naphthalene-ring, single-benzene-ring, and completely ring-opened products. Reactive oxygen species on anatase TiO2 surface, such as O2-• and O2-, contributed to oxidative degradation. Based on these findings, a novel oxidation degradation mechanism was proposed. The reaction at (101) surface of anatase TiO2 was used as a model. The naphthalene-ring oxidative products with chloronaphthols and hydroxyl-pentachloronaphthalene-dione, could be formed via attacking the carbon of naphthalene ring at one or more positions by nucleophilic O2-. Lateral cleavage of the naphthalene ring at different C1-C10 and C4-C9, C1-C2 and C4-C9, C1-C2 or and C3-C4 bond positions by electrophilic O2-• could occur. This will lead to the formation of tetrachlorophenol, tetrachloro-benzoic acid, tetrachloro-phthalaldehyde, and tetrachloro-acrolein-benzoic acid, partially with further transformation into tetrachlorobenzene-dihydrodiol and tetrachloro-salicylic acid. Unexpectedly, the symmetric half section of CN-75 could be completely remained with generating the intricate oxidative intermediates characteristically containing tetrachlorobenzene structure. Complete cleavage of naphthalene ring could produce the ring-opened products, such as formic and acetic acids.

  3. Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review.

    Science.gov (United States)

    Xu, Haomiao; Yan, Naiqiang; Qu, Zan; Liu, Wei; Mei, Jian; Huang, Wenjun; Zhao, Songjian

    2017-08-15

    Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. Mn-based oxides can be classified into four types: (1) single manganese oxide (MnOx), (2) supported manganese oxide (MnOx/support), (3) composite manganese oxides (MnOx-X), and (4) special crystalline manganese oxides (S-MnOx). These Mn-based oxides have been widely used as catalysts for the elimination of gaseous pollutants. This review aims to describe the environmental applications of these manganese oxides and provide perspectives. It gives detailed descriptions of environmental applications of the selective catalytic reduction of NOx with NH 3 , the catalytic combustion of volatile organic compounds, Hg 0 oxidation and adsorption, and soot oxidation, in addition to some other environmental applications. Furthermore, this review mainly focuses on the effects of structure, morphology, and modified elements and on the role of catalyst supports in gaseous heterogeneous catalytic reactions. Finally, future research directions for developing manganese oxide catalysts are proposed.

  4. CATALYTIC OXIDATION OF AIR POLLUTANTS FROM PULP AND PAPER INDUSTRY USING OZONE

    Science.gov (United States)

    Major pollutants from pulp and paper mills include volatile organic compounds (VOCs) such as methanol and total reduced sulfur compounds (TRS) such as dimethyl sulfide. The conventional treatment technologies including incineration or catalytic thermal oxidation are energy intens...

  5. Next Generation Hybrid Photo-Catalytic Oxidation (PCO) for Trace Contaminant Control

    Data.gov (United States)

    National Aeronautics and Space Administration — Photocatalytic oxidation (PCO) is a primary candidate as an alternative to thermal-catalytic or sorbent- based technologies for VOC trace contaminant control due to...

  6. The decomposition of mixed oxide Ag2Cu2O3: Structural features and the catalytic properties in CO and C2H4 oxidation

    Science.gov (United States)

    Svintsitskiy, Dmitry A.; Kardash, Tatyana Yu.; Slavinskaya, Elena M.; Stonkus, Olga A.; Koscheev, Sergei V.; Boronin, Andrei I.

    2018-01-01

    The mixed silver-copper oxide Ag2Cu2O3 with a paramelaconite crystal structure is a promising material for catalytic applications. The as-prepared sample of Ag2Cu2O3 consisted of brick-like particles extended along the [001] direction. A combination of physicochemical techniques such as TEM, XPS and XRD was applied to investigate the structural features of this mixed silver-copper oxide. The thermal stability of Ag2Cu2O3 was investigated using in situ XRD under different reaction conditions, including a catalytic CO + O2 mixture. The first step of Ag2Cu2O3 decomposition was accompanied by the appearance of ensembles consisting of silver nanoparticles with sizes of 5-15 nm. Silver nanoparticles were strongly oriented to each other and to the surface of the initial Ag2Cu2O3 bricks. Based on the XRD data, it was shown that the release of silver occurred along the a and b axes of the paramelaconite structure. Partial decomposition of Ag2Cu2O3 accompanied by the formation of silver nanoparticles was observed during prolonged air storage under ambient conditions. The high reactivity is discussed as a reason for spontaneous decomposition during Ag2Cu2O3 storage. The full decomposition of the mixed oxide into metallic silver and copper (II) oxide took place at temperatures higher than 300 °C regardless of the nature of the reaction medium (helium, air, CO + O2). Catalytic properties of partially and fully decomposed samples of mixed silver-copper oxide were measured in low-temperature CO oxidation and C2H4 epoxidation reactions.

  7. Role of iron oxide catalysts in selective catalytic reduction of NOx and soot from vehicular emission

    International Nuclear Information System (INIS)

    Anjuman, S.; Tahira, S.; Hizbullah, K.; Hizbullah, K.

    2011-01-01

    This study deals with Iron containing catalysts i.e Iron oxide Fe/sub 2/O/sub 3/) Iron potassium oxide Fe/sub 1.9/K/sub 0.1/O/sub 3/, copper iron oxide Cu/sub 0.9/K/sub 0.1/, Fe/sub 2/O/sub 3/, nickel iron oxide Ni Fe/sub 2/O/sub 4/, and Nickel potassium iron oxide Ni/sub 0.95/K/sub 0.05/ Fe/sub 2/O/sub 4/ catalyst were synthesized by using PVA technique. By X-ray Diffraction technique these catalysts were characterized to ensure the formation of crystalline structure. Energy Dispersive X-rays analysis (EDX) was used for the confirmation of presence of different metals and Scanning Electron Microscopy (SEM) for Surface Morphology. Then the catalytic investigations of the prepared catalyst were carried out for their activity measurement toward simultaneous conversion of NOx and Soot from an engine exhaust. Some Iron containing oxide catalysts were partially modified by alkali metal potassium and were used for NOx -Soot reaction in a model exhaust gas. Fe/sub 1.9 K /sub 0.1/O/sub 3/ show high catalytic performance for N/sub 2/ formation in the prepared catalyst. Further studies have shown that Fe/sub 1.9/ K/sub 0.1/ O/sub 3/ was deactivated in a substantial way after about 20 Temperature. Temperature Programmed Reaction (TPR) experiments due to agglomeration of the promoter potassium. Experiments carried out over the aged Fe/sub 1.9/K/sub 0.1/O/sub 3/ catalyst have shown that NOx-soot reaction was suppressed at higher oxygen concentration, since O/sub 2/-soot conversion was kindly favored. More over nitrite species formed at the catalyst surface might play an important role in NOx-soot conversion. (author)

  8. Catalytic decomposition of N2O on ordered crystalline metal oxides.

    Science.gov (United States)

    Ma, Zhen; Ren, Yu; Lu, Yanbin; Bruce, Peter G

    2013-07-01

    The synthesis of mesoporous metal oxides using mesoporous silicas or carbons as hard templates has attracted growing interest recently, but the catalytic application of mesoporous metal oxides has not been studied sufficiently. In addition, few publications have compared the catalytic performance of a series of mesoporous metal oxides in the same reaction, and little is known about the influence of preparation details of mesoporous metal oxides on catalytic activity. Herein, ordered crystalline mesoporous metal oxides (i.e., CeO2, Co3O4, Cr2O3, CuO, alpha-Fe2O3, beta-MnO2, Mn2O3, Mn3O4, NiO) prepared using mesoporous SiO2 (KIT-6) as a hard template were tested in the decomposition of N2O, an environmental pollutant, and the catalytic performance was compared with that of commercial metal oxides with low surface areas. In particular, mesoporous Co3O4, beta-MnO2, and NiO showed high N2O conversions at 350 degrees C. The influence of preparation parameters of mesoporous Co3O4 on catalytic activity was then studied in more detail. Mesoporous Co3O4 samples with different pore sizes and wall thicknesses were prepared using KIT-6 synthesized under different hydrothermal or calcination temperatures. Interestingly, the catalytic activities of different mesoporous Co3O4 samples were found to be influenced by these preparation details.

  9. Partial oxidation of n- and i-pentane over promoted vanadium-phosphorus oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A.; Mikhajluk, B.D.; Komashko, G.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    It is known, that the cost of raw materials for catalytic oxidation processes is about 60% of the product price. Cheap initial compounds to produce variety of products and to replace olefins and aromatic hydrocarbons are paraffins. That is why catalytic systems which could be possibly rather efficient in selective oxidation of paraffin hydrocarbons are under very close investigation now. One of such processes in n-pentane oxidation. The obtained results on n-pentane oxidation over VPO catalysts were quite encouraging in respect of possible reach high selectivity and yield of phthalic anhydride. However, in our work it was shown that the main product of n-pentane oxidation in the presence of VPO catalytic system as well as VPMeO was maleic anhydride. Some later our results were confirmed in, where to grow the selectivity towards phthalic anhydride the Co-additive was introduced. On the basis of the proposal made before on the mechanism of paraffins conversion over the vanadyl pyrophosphate surface with their activation at the first and fourth carbon atoms, we assumed possible methylmaleic (citraconic) anhydride forming at n- and i-pentane oxidation. This assumption has been recently supported by both our and other researchers` experimental results. In it was also hypothized possible mechanistic features for phthalic anhydride forming from n-pentane. The present work deals with the results of n- and i-pentane oxidation over VPO catalysts promoted with Bi, Cs, Te, Zr. (orig.)

  10. Catalytic soot oxidation over Ce- and Cu-doped hydrotalcites-derived mesoporous mixed oxides.

    Science.gov (United States)

    Wang, Zhongpeng; Wang, Liguo; He, Fang; Jiang, Zheng; Xiao, Tiancun; Zhang, Zhaoliang

    2014-09-01

    Ce- and Cu-doped hydrotalcites derived mixed oxides were prepared through co-precipitation and calcination method, and their catalytic activities for soot oxidation with O2 and O2/NO were investigated. The solids were characterized by XRD, TG-DTG, BET, H2-TPR, in situ FTIR and TPO techniques. All the catalysts precursors showed the typical diffraction patterns of hydrotalcite-like materials having layered structure. The derived mixed oxides exhibited mesoporous properties with specific surface area of 45-160 m2/g. After both Ce and Cu incorporated, mixed crystalline phases of CuO (tenorite), CeO2 (fluorite) and MgAl2O4 (spinel) were formed. As a result, the NO(x) adsorption capacity of this catalyst was largely increased to 201 μmol/g, meanwhile, it was also the most effective to convert NO into NO2 in the sorption process due to the enhanced reducibility. The in situ FTIR spectra revealed that NO(x) were stored mainly as chelating bidentate and monodentate nitrate. The interaction effect between Cu and Ce in the mixed oxide resulted in different NO(x) adsorption behavior. Compared with the non-catalyzed soot oxidation, soot conversion curves over the mixed oxides catalysts shift to low temperature in O2. The presence of NO in the gas phase significantly enhanced the soot oxidation activity with ignition temperature decreased to about 320 degrees C, which is due to NO conversion to NO2 over the catalyst followed by the reaction of NO2 with soot. This explains the cooperative effect of Ce and Cu in the mixed oxide on soot oxidation with high activity and 100% selectivity to CO2 formation.

  11. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    International Nuclear Information System (INIS)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei

    2014-01-01

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H 2 O 2 ) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS 4 )) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS 4 ). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS 4 )/H 2 O 2 was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS 4 )/H 2 O 2 system

  12. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  13. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  14. The catalytic oxidation of organic contaminants in a packed bed reactor

    NARCIS (Netherlands)

    van de Beld, L.; Bijl, M.P.G.; Reinders, A.; van der Wert, B.; Westerterp, K.R.

    1994-01-01

    The catalytic oxidation of several hydrocarbons was studied over noble metal and metal oxide catalysts. A fast empirical method was developed to determine the minimum operating temperature required to guarantee complete conversion of the hydrocarbon. The influence of the operating parameters such as

  15. Kinetic studies of isooctane partial oxidation over a nickel-based catalyst

    International Nuclear Information System (INIS)

    Ibrahim, Hussameldin; Idem, Raphael; Aboudheir, Ahmed

    2006-01-01

    The production of hydrogen (H 2 ) for fuel cell applications in mobile vehicles by reforming technologies such as partial oxidation of various fossil fuels has gained much attention recently. In this study, the production of H 2 by the catalytic partial oxidation of isooctane ((C 8 H 18 ) used here as a surrogate for gasoline) was investigated over alumina (AI 2 O 3 )supported nickel (Ni) catalyst. The work investigated the kinetics of the partial oxidation of isooctane over a stable Ni/□-AI 2 O 3 catalyst in the range of 863 to 913 K, at atmospheric pressure, W/F i c8 in the range of 1.97 to 8.58 g h mol - 1, and molar feed ratio in the range of 2.0 to 8.0 experiments to obtain kinetic data were performed in a 12.7 mm diameter Inconel micro-reactor housed in an electrically controlled furnace. The chemical reaction was then modeled using rate models developed from the Langmuir-Hinshelwood-hougen-Watson (LHHW) and Eley-Rideal (ER) formulations. The model parameters were estimated using an adaptive Gauss-Newton and Marquardi-Levenberg minimization algorithm. Rival models were screened for their thermodynamic consistency and physicochemical significance of estimated parameters. Langmuir-Hinshelwood-hougen-Watson mechanism requiring the dissociative adsorption of isooctane and oxygen on two different sites appeared to be the most likely pathway for the partial oxidation reaction of isooctane. Reaction order with respect to isooctane indicates the strong coverage of nickel by isooctane. The activation energy of 73±3.1 kJ mol - 1 estimated from the LHHW model is consistent with the trend observed with lower hydrocarbons.(Author)

  16. Selective Catalytic Oxidation of NH3 to N2 for Catalytic Combustion of Low Heating Value Gas under Lean/Rich Conditions

    Czech Academy of Sciences Publication Activity Database

    Kušar, H.M.J.; Ersson, A.G.; Vosecký, Martin; Järas, S.G.

    2005-01-01

    Roč. 58, 1-2 (2005), s. 25-32 ISSN 0926-3373 Institutional research plan: CEZ:AV0Z40720504 Keywords : catalytic combustion * selective catalytic oxidation * ammonia Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.809, year: 2005

  17. Oxidative stress and partial migration in brown trout (Salmo trutta)

    DEFF Research Database (Denmark)

    Birnie-Gauvin, Kim; Peiman, K. S.; Larsen, Martin Hage

    2017-01-01

    During migration, animals are typically limited by their endogenous energetic resources which must be allocated to the physiological costs associated with locomotion, as well as avoiding and/or compensating for oxidative stress. To date, there have been few attempts to understand the role...... oxidative stress and migration. Using the brown trout, we obtained blood samples from juveniles from a coastal stream in Denmark in the fall prior to peak seaward migration which occurs in the spring, and assayed for antioxidant capacity (oxygen radical absorbance capacity) and oxidative stress levels...... of oxidative status in migration biology, particularly in fish. Semi-anadromous brown trout (Salmo trutta, Linnaeus 1758) exhibit partial migration, where some individuals smoltify and migrate to sea, and others become stream residents, providing us with an excellent model to investigate the link between...

  18. Biodiesel by catalytic reactive distillation powered by metal oxides

    NARCIS (Netherlands)

    Kiss, A.A.; Dimian, A.C.; Rothenberg, G.

    2008-01-01

    The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current production processes are outlined. A novel sustainable esterification process based on catalytic reactive distillation is proposed. The pros and cons of manufacturing biodiesel via fatty acid

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

    Indian Academy of Sciences (India)

    Administrator

    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 ... clean inter conversion between tetramer and monomer complex using elemental sulfur ...

  20. Catalytic oxidative pyrolysis of spent organic ion exchange resins from nuclear power plants

    International Nuclear Information System (INIS)

    Sathi Sasidharan, N.; Deshingkar, D.S.; Wattal, P.K.; Shirsat, A.N.; Bharadwaj, S.R.

    2005-08-01

    The spent IX resins from nuclear power reactors are highly active solid wastes generated during operations of nuclear reactors. Catalytic oxidative pyrolysis of these resins can lead to high volume reduction of these wastes. Low temperature pyrolysis of transition metal ion loaded IX resins in presence of nitrogen was carried out in order to optimize catalyst composition to achieve maximum weight reduction. Thermo gravimetric analysis of the pyrolysis residues was carried out in presence of air in order to compare the oxidative characteristics of transition metal oxide catalysts. Copper along with iron, chromium and nickel present in the spent IX resins gave the most efficient catalyst combination for catalytic and oxidative pyrolysis of the residues. During low temperature catalytic pyrolysis, 137 Cesium volatility was estimated to be around 0.01% from cationic resins and around 0.1% from anionic resins. During oxidative pyrolysis at 700 degC, nearly 10 to 40% of 137 Cesium was found to be released to off gases depending upon type of resin and catalyst loaded on to it. The oxidation of pyrolytic residues at 700 degC gave weight reduction of 15% for cationic resins and 93% for anionic resins. Catalytic oxidative pyrolysis is attractive for reducing weight and volume of spent cationic resins from PHWRs and VVERs. (author)

  1. Catalytic oxidant scavenging by selenium-containing compounds

    DEFF Research Database (Denmark)

    Carroll, Luke; Pattison, David I; Fu, Shanlin

    2017-01-01

    Myeloperoxidase produces strong oxidants during the immune response to destroy invading pathogens. However, these oxidants can also cause tissue damage, which contributes to the development of numerous inflammatory diseases. Selenium containing compounds, including selenomethionine (SeMet) and 1,...

  2. Catalytic ozonation of sulfamethoxazole by composite iron-manganese silicate oxide: cooperation mechanism between adsorption and catalytic reaction.

    Science.gov (United States)

    Gao, Guoying; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Chu, Wei

    2016-11-01

    A systematic investigation of the cooperation mechanism between adsorption and catalytic reaction during the catalytic ozonation of sulfamethoxazole (SMX) by composite iron-manganese silicate oxide (FMSO) was carried out in this work. Results showed that the total organic carbon (TOC) removal increased significantly from 27 % (sole-ozonation) to 79.8 % (FMSO catalytic ozonation). The presence of FMSO in the ozonation process effectively enhanced the ozone utilization efficiency and accelerated the transformation of ozone into hydroxyl radicals. The latter result was verified by the indirect method, using NaHSO 3 as the reductor, and the direct electron spin resonance (ESR) determination technology. The adsorption of SMX on FMSO was minimal (1.8 %). However, ozone rapidly converted SMX into various intermediates, which was exhibited by the much higher adsorption affinity on the surface of FMSO than that of SMX. The accumulation of various intermediates on the FMSO surface also increased their contact probability with the ·OH radicals generated by the ozone decomposition. The continuous interaction of intermediates with ·OH radicals could further promote the benign cycling of the release of adsorption sites and the succeeding adsorption/decomposition of ozone and intermediates on FMSO. This could be another reason for the higher and faster TOC removal rate.

  3. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    acer

    ABSTRACT: Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate ...

  4. Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

    African Journals Online (AJOL)

    Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate constant and ...

  5. CATALYTIC RECOMBINATION OF RADIOLYTIC GASES IN THORIUM OXIDE SLURRIES

    Science.gov (United States)

    Morse, L.E.

    1962-08-01

    A method for the coinbination of hydrogen and oxygen in aqueous thorium oxide-uranium oxide slurries is described. A small amount of molybdenum oxide catalyst is provided in the slurry. This catalyst is applicable to the recombination of hydrogen and/or deuterium and oxygen produced by irradiation of the slurries in nuclear reactors. (AEC)

  6. Nickel/alumina catalysts modified by basic oxides for the production of synthesis gas by methane partial oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Requies, J.; Cabrero, M.A.; Barrio, V.L.; Cambra, J.F.; Gueemez, M.B.; Arias, P.L. [School of Engineering (UPV/EHU), Department of Chemical and Environmental Engineering, 48013 Bilbao (Spain); La Parola, V.; Pena, M.A.; Fierro, J.L.G. [Institute of Catalysis and Petrochemistry, CSIC, Cantoblanco, 28049 Madrid (Spain)

    2006-08-15

    In the present work, Ni/{alpha}-Al{sub 2}O{sub 3} catalysts modified with different amounts of CaO and MgO were used for the production of hydrogen by catalytic partial oxidation (CPO) and wet-CPO processes of methane. In the wet-CPO process, small additions of water were introduced into the feed of the reactor to improve both the H{sub 2} yield and methane conversion. The addition of water is also beneficial because coke formation becomes thermodynamically unfavorable. The catalysts were characterized before and after the reaction with XRD, XPS, TPR and TPO techniques. Several methane decomposition tests and methane pulse experiments were carried out with a view to correlating the ability of metal sites to activate methane in the absence of oxygen with the performance for CPO and wet-CPO reactions. (author)

  7. Bimetallic Cu-Ni nanoparticles supported on activated carbon for catalytic oxidation of benzyl alcohol

    Science.gov (United States)

    Kimi, Melody; Jaidie, Mohd Muazmil Hadi; Pang, Suh Cem

    2018-01-01

    A series of bimetallic copper-nickel (CuNix, x = 0.1, 0.2, 0.5 and 1) nanoparticles supported on activated carbon (AC) were prepared by deposition-precipitation method for the oxidation of benzyl alcohol to benzaldehyde using hydrogen peroxide as oxidising agent. Analyses by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) confirmed that Cu and Ni was successfully added on the surface of activated carbon. CuNi1/AC showed the best catalytic activity for the oxidation of benzyl alcohols to the corresponding aldehyde within a short reaction period at 80 °C. The catalytic performance is significantly enhanced by the addition of equal amount of Ni as compared to the monometallic counterpart. This result indicates the synergistic effect between Ni and Cu particles in the catalytic oxidation reaction.

  8. Session 6: Water depollution from aniline and phenol by air oxidation and adsorptive-catalytic oxidation in liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Dobrynkin, N.M.; Batygina, M.V.; Noskov, A.S. [Boreskov Institute of Catalysis of Siberian Branch of Russian Academy of Sciences, Pr. Ak. Lavrentieva (Russian Federation)

    2004-07-01

    This paper is devoted to development of carbon catalysts and application of catalytic wet air oxidation for deep cleaning of polluted waters. The described catalysts and method are solving the problem of development environmentally reliable method for fluids treatment and allow carrying out the adsorption of pollutants on carbon CAPM (catalytically active porous material) with following regeneration of the CAPM without the loss of adsorptive qualities. The experiments have shown a principal capability simultaneously to use carbon CAPM as adsorbent and either as catalyst, or as a catalyst support for oxidation of aniline and phenol in water solutions. (authors)

  9. Co2 Effect on the Catalytic Behavior of Alumina Supported Mixed Oxides

    International Nuclear Information System (INIS)

    Aouissi, A.; Aldhayan, D.; Mahdjoubi, H.A.

    2005-01-01

    The industrial catalysts for the reforming reactions suffer from coke which accelerates their deactivation. One of the remedy is to adjust the partial pressure of hydrogen. This work is focused on the work of CO2 on the total conversion of n-heptane and on its cyclization reaction into cyclohexane. The tests were carried out over a series of bifunctional catalysts constituted of mixed oxides supported on alumina. The catalysts, which are prepared by co-precipitation method, were characterized by means of atomic absorption spectroscopy and Fourier-transformed infrared spectroscopy (FTIR). Catalytic tests were carried out with and without carbon dioxide under atmospheric pressure. Results indicate that carbon dioxide influences the total activity of the catalysts and selectivity to form cyclohexane. So that, at 250C, the total conversion was high but the cyclohexane selectivity was low. In the range 250C-450C, results indicate an increase of both conversion and selectivity due to temperature increase, but fast deactivation was observed due to coke formation which can be removed by CO2 at higher temperatures. (author)

  10. Catalytic properties of nickel ferrites for oxidation of glucose, β-nicotiamide adenine dinucleotide (NADH) and methanol

    Energy Technology Data Exchange (ETDEWEB)

    Galindo, R. [Departamento de Química, Universidad de Guanajuato, Cerro de la Venada s/n, Pueblito de Rocha, C.P. 36040 Guanajuato, Gto (Mexico); Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain); Gutiérrez, S. [Departamento de Química, Universidad de Guanajuato, Cerro de la Venada s/n, Pueblito de Rocha, C.P. 36040 Guanajuato, Gto (Mexico); Menéndez, N. [Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain); Herrasti, P., E-mail: pilar.herrasti@uam.es [Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, Cantoblanco s/n, C.P. 28049 Madrid (Spain)

    2014-02-15

    Highlights: ► NiFe{sub 2}O{sub 4} nanoparticles obtained by electrochemical method are effective catalyst. ► A partially inverse spinel was obtained with 57% Fe{sup 3+} in tetrahedral position. ► A non-enzymatic electrode using NiFe{sub 2}O{sub 4} nanoparticles has been manufactured. -- Abstract: Nickel ferrite nanoparticles (NiFe{sub 2}O{sub 4}) were synthesized by electrochemical method and used as catalyst for direct oxidation of glucose, NADH and methanol. Characterization of these nanoparticles was carried out by X-ray diffraction, Mössbauer spectroscopy, and colloidal properties such as hydrodynamic radius and Zeta potential. To evaluate the catalytic properties of these nanoparticles against the oxidation process, paste graphite electrodes mixing nickel ferrites and different conductive materials (graphite, carbon nanotubes) and binders agents (mineral oil, 1-octylpyridinium hexafluorophosphate (nOPPF6)) were used. The results prove good catalytic properties of these materials, with an oxidation potential around 0.75, 0.5 and 0.8 V for glucose, NADH, and methanol, respectively.

  11. Iron oxides and their applications in catalytic processes: a review

    OpenAIRE

    Oliveira, Luiz C. A.; Fabris, José D.; Pereira, Márcio C.

    2013-01-01

    A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more...

  12. Kinetic and catalytic analysis of mesoporous Co3O4 on the oxidation of morin

    Science.gov (United States)

    Xaba, Morena. S.; Meijboom, Reinout

    2017-11-01

    Herein we report on the synthesis, characterization and catalytic evaluation of mesoporous cobalt oxides on the oxidation of morin. These mesoporous cobalt oxides were synthesized using an inverse surfactant micelle method, they are connected, well-defined with intra-particle voids. These materials were calcined to different final heating temperatures of 150, 250, 350, 450 and 550 °C, and each mesoporous cobalt oxide catalyst showed unique physical properties and catalytic behavior. Morin oxidation was used as a model reaction in the presence of hydrogen peroxide to evaluate the kinetic and catalytic activity of calcined mesoporous cobalt oxides. The adsorption-desorption equilibrium rate constants of morin and hydrogen peroxide were found to be inversely proportional to the crystallite size of the mesoporous cobalt oxide, and the characteristic path length in which the mass transfer takes place was found to be directly proportional to the crystallite size. The materials were characterized using powder X-Ray Diffraction (p-XRD), N2-sorption isotherms (BET), hydrogen temperature programmed reduction (H2-TPR) and High Resolution-Transmission Electron Microscopy (HR-TEM). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of morin at λmax = 410 nm. The surface reaction in this system is described in terms of the well-established Langmuir-Hinshelwood model. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability is demonstrated.

  13. Reactor modeling and process analysis for partial oxidation of natural gas

    NARCIS (Netherlands)

    Albrecht, B.A.

    2004-01-01

    This thesis analyses a novel process of partial oxidation of natural gas and develops a numerical tool for the partial oxidation reactor modeling. The proposed process generates syngas in an integrated plant of a partial oxidation reactor, a syngas turbine and an air separation unit. This is called

  14. The chemical energy unit partial oxidation reactor operation simulation modeling

    Science.gov (United States)

    Mrakin, A. N.; Selivanov, A. A.; Batrakov, P. A.; Sotnikov, D. G.

    2018-01-01

    The chemical energy unit scheme for synthesis gas, electric and heat energy production which is possible to be used both for the chemical industry on-site facilities and under field conditions is represented in the paper. The partial oxidation reactor gasification process mathematical model is described and reaction products composition and temperature determining algorithm flow diagram is shown. The developed software product verification showed good convergence of the experimental values and calculations according to the other programmes: the temperature determining relative discrepancy amounted from 4 to 5 %, while the absolute composition discrepancy ranged from 1 to 3%. The synthesis gas composition was found out practically not to depend on the supplied into the partial oxidation reactor (POR) water vapour enthalpy and compressor air pressure increase ratio. Moreover, air consumption coefficient α increase from 0.7 to 0.9 was found out to decrease synthesis gas target components (carbon and hydrogen oxides) specific yield by nearly 2 times and synthesis gas target components required ratio was revealed to be seen in the water vapour specific consumption area (from 5 to 6 kg/kg of fuel).

  15. Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

    Science.gov (United States)

    Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

    2013-04-23

    As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

  16. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    Science.gov (United States)

    Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

    2016-06-01

    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  17. Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp [International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp [Department of Hydrogen Energy Systems, Faculty of Engineering, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan); International Research Center for Hydrogen Energy, Kyushu University Motooka 744, Nishiku, Fukuoka, 810-0395 (Japan)

    2016-06-03

    Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

  18. Catalytic role of transition metals supported on niobium oxide in O2 activation

    Science.gov (United States)

    Omidvar, Akbar

    2018-03-01

    Metal particles supported on metal oxides (MMO) are promising materials with versatile applications such as catalyst in fuel cell technologies. As one of the transition metal oxides, niobium oxide (NbO) demonstrates a wide interesting properties that make it a potentially applicable in MMO materials. Here, the catalytic activity for the O2 activation of transition metals (Fe, Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) supported on the NbO has been studied theoretically using density functional theory (DFT). The activation of O2 molecule and yielding two separated O atoms is an essential step for the oxygen reduction reaction. Our study demonstrates that the transition metals supported on the NbO can act as driving force for O2 dissociation. Consistent with the prediction of reactivity descriptors, the maximum catalytic activity toward O2 activation is related to the Pt-supported on the NbO metal oxide.

  19. Green chemicals from pulp production black liquor by partial wet oxidation.

    Science.gov (United States)

    Muddassar, Hassan Raja; Melin, Kristian; de Villalba Kokkonen, Daniela; Riera, Gerard Viader; Golam, Sarwar; Koskinen, Jukka

    2015-11-01

    To reduce greenhouse gas emissions, more sustainable sources of energy, fuel and chemicals are needed. Biomass side streams such as black liquor, which is a by-product of pulp production, has the potential to be used for this purpose. The aim of the study was the production of carboxylic acids, such as lactic acid, formic acid and acetic acid, from kraft and non-wood black liquor. The processes studied were partial wet oxidation (PWO) and catalytic partial wet oxidation (CPWO). The results show that the yield of carboxylic acid is higher when treated by PWO than the results from CPWO at temperatures of 170 °C and 230 °C. The results shows that the PWO process can increase the yield of carboxylic acids and hydroxy acids in black liquor, reduce lignin content and decrease pH, which makes further separation of the acids more favourable. The hydroxy acids are valuable raw materials for biopolymers, and acetic acid and formic acid are commonly used chemicals conventionally produced from fossil feedstock. © The Author(s) 2015.

  20. Gold & silver nanoparticles supported on manganese oxide: Synthesis, characterization and catalytic studies for selective oxidation of benzyl alcohol

    OpenAIRE

    Alabbad, Saad; Adil, S.F.; Assal, M.E.; Khan, Mujeeb; Alwarthan, Abdulrahman; Siddiqui, M. Rafiq H.

    2014-01-01

    Nano-gold and silver particles supported on manganese oxide were synthesized by the co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as a source of oxygen. The catalyst was calcined at 300, 400 and 500 °C. They were characterized by electron microscopy, powder X-ray diffraction (XRD) and surface area. It was observed that the calcination temperature affects the size of the nanoparticle, which play...

  1. Catalytic oxidation of phosphorus on MoO3 as studied by infrared spectroscopy

    International Nuclear Information System (INIS)

    Paul, D.K.; Rao, L.F.; Yates, J.T. Jr.

    1992-01-01

    Transmission infrared spectroscopy and mass spectroscopy were used to study the decomposition and oxidation of phosphine on an MoO 3 /Al 2 O 3 supported catalyst at 300-800 K. At 573 K, phosphine decomposes and is oxidized to a HP=O surface species. At 673 K, further oxidation forms (HO) x P=O that desorbs from the surface around 773 K. This suggests that the MoO 3 /Al 2 O 3 catalyst may be useful for continuous organophosphorous catalytic oxidation. 30 refs., 12 figs., 1 tab

  2. Bulk Preparation of Holey Graphene via Controlled Catalytic Oxidation

    Science.gov (United States)

    Watson, Kent (Inventor); Lin, Yi (Inventor); Ghose, Sayata (Inventor); Connell, John (Inventor)

    2015-01-01

    A scalable method allows preparation of bulk quantities of holey carbon allotropes with holes ranging from a few to over 100 nm in diameter. Carbon oxidation catalyst nanoparticles are first deposited onto a carbon allotrope surface in a facile, controllable, and solvent-free process. The catalyst-loaded carbons are then subjected to thermal treatment in air. The carbons in contact with the carbon oxidation catalyst nanoparticles are selectively oxidized into gaseous byproducts such as CO or CO.sub.2, leaving the surface with holes. The catalyst is then removed via refluxing in diluted nitric acid to obtain the final holey carbon allotropes. The average size of the holes correlates strongly with the size of the catalyst nanoparticles and is controlled by adjusting the catalyst precursor concentration. The temperature and time of the air oxidation step, and the catalyst removal treatment conditions, strongly affect the morphology of the holes.

  3. Waste Not, Want Not: Mild and Selective Catalytic Oxidation of Uronic Acids

    NARCIS (Netherlands)

    Klis, van der F.; Frissen, A.E.; Haveren, van J.; Es, van D.S.

    2013-01-01

    And isn't it uronic: A mild, highly efficient and selective catalytic oxidation of pectin-derived uronic acids to the corresponding aldaric acids is reported. Fast, quantitative conversions (>99%) of the starting materials are achieved with high selectivity (>97%) at room temperature, using

  4. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  5. Tritium removal from air streams by catalytic oxidation and water adsorption

    International Nuclear Information System (INIS)

    Sherwood, A.E.

    1976-06-01

    An effective method of capturing tritium from air streams is by catalytic oxidation followed by water adsorption on a microporous solid adsorbent. Performance of a burner/dryer combination is illustrated by overall mass balance equations. Engineering design methods for packed bed reactors and adsorbers are reviewed, emphasizing the experimental data needed for design and the effect of operating conditions on system performance

  6. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    Science.gov (United States)

    Pence, Dallas T.; Thomas, Thomas R.

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  7. Catalytic oxidation of cyanides in an aqueous phase over individual and manganese-modified cobalt oxide systems

    International Nuclear Information System (INIS)

    Christoskova, St.; Stoyanova, M.

    2009-01-01

    The possibility for purification of wastewaters containing free cyanides by applying of a new method based on cyanides catalytic oxidation with air to CO 2 and N 2 at low temperature and atmospheric pressure was investigated. On this purpose, individual and modified with manganese Co-oxide systems as active phase of environmental catalysts were synthesized. The applied method of synthesis favours the preparation of oxide catalytic systems with high active oxygen content (total-O* and surface-O* s ) possessing high mobility, and the metal ions being in a high oxidation state and in an octahedral coordination-factors determining high activity in reactions of complete oxidation. The catalysts employed were characterized by powder X-ray diffraction, Infrared spectroscopy, and chemical analysis. The effect of pH of the medium and catalyst loading on the effectiveness of the cyanide oxidation process, expressed by the degree of conversion (α, %), by the rate constant (k, min -1 ), and COD was studied. The results obtained reveal that using catalysts investigated a high cyanide removal efficiency could be achieved even in strong alkaline medium. The higher activity of the manganese promoted catalytic sample could be explained on the basis of higher total active oxygen content and its higher mobility both depending on the conditions, under which the synthesis of catalyst is being carried out.

  8. Laser-induced partial oxidation of cyclohexane in liquid phase

    International Nuclear Information System (INIS)

    Oshima, Y.; Wu, X.W.; Koda, S.

    1995-01-01

    A laser-induced partial oxidation of cyclohexane was studied in the liquid phase. With KrF excimer laser (248 nm) irradiation to neat liquid cyclohexane in which O 2 was dissolved, cyclohexanol and cyclohexanone were obtained with very high selectivities, together with cyclohexane as a minor product. Radical recombination reactions to produce dicyclohexyl ether and bicyclohexyl also took place, while these products were not observed in the gas phase reaction. These experimental results were considered to be due not only to higher concentration of cyclohexane but to the cage effect in the liquid phase oxidation. To clarify the reaction progress including the photoabsorption process, the effects of laser intensity and O 2 pressure on product distribution were studied. (author)

  9. A Decrease in NiO-MgO Phase Through Its Solid Solution Equilibrium with Tetragonal (La1−zSrz2Ni1−yMgyO4−δ: Effect on Catalytic Partial Oxidation of Methane

    Directory of Open Access Journals (Sweden)

    Xiong Yin

    2012-01-01

    Full Text Available Calcination of an oxide mixture consisting of 0.4 La2O3, 0.2 SrCO3, (1−xNiO, and xMgO at 800∘C results in an equilibrium between tetragonal (La1−zSrz2Ni1−yMgyO4−δ phase and NiO-MgO phase. Forming rock-salt NiO-MgO facilitates the NiO to join the tetragonal phase. The size of the NiO-MgO phase in the resulting composite is reduced with the increase in MgO (the x value. The composite thus obtained is used to catalyze partial oxidation of methane, and the maximum methane conversion of ca. 93% is achieved when x=0.2. A further rise in x value results in a monotonic decrease in the methane conversion. X-ray diffraction, electron microscopy, and chemosorption all confirm a decrease in both size and amount of the supported Ni0 clusters with the increase in MgO dosage. The reduction in size promotes the dispersion of Ni0 sites and gives rise to both high activity and strong coking resistance.

  10. Catalytic routes and oxidation mechanisms in photoreforming of polyols

    Energy Technology Data Exchange (ETDEWEB)

    Sanwald, Kai E.; Berto, Tobias F.; Eisenreich, Wolfgang; Gutiérrez, Oliver Y.; Lercher, Johannes A.

    2016-12-01

    Photocatalytic reforming of biomass-derived oxygenates leads to H2 generation and evolution of CO2 via parallel formation of organic intermediates through anodic oxidations on a Rh/TiO2 photocatalyst. The reaction pathways and kinetics in the photoreforming of C3–C6 polyols were explored. Polyols are converted via direct and indirect hole transfer pathways resulting in (i) oxidative rupture of C–C bonds, (ii) oxidation to a-oxygen functionalized aldoses and ketoses (carbonyl group formation) and (iii) light-driven dehydration. Direct hole transfer to chemisorbed oxygenates on terminal Ti(IV)-OH groups, generating alkoxy-radicals that undergo ß-C–C-cleavage, is proposed for the oxidative C–C rupture. Carbonyl group formation and dehydration are attributed to indirect hole transfer at surface lattice oxygen sites [Ti_ _ _O_ _ _Ti] followed by the generation of carbon-centered radicals. Polyol chain length impacts the contribution of the oxidation mechanisms favoring the C–C bond cleavage (internal preferred over terminal) as the dominant pathway with higher polyol carbon number.

  11. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  12. Catalytic oxidative conversion of alkanes to olefines and oxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    All of the direct reaction schemes described and the corresponding process schemes are still in an exploratory state. Ethylene by oxidative coupling of methane could become competitive if process schemes are developed with significantly less expenditures for separation of the product from unconverted feed. No encouragement for formaldehyde from methane can be presently derived from the existing knowledge. Liquid-phase oxidation of methane to methanol appears to be attractive but no final judgement is possible at present. Oxidative dehydrogenation of ethylene and propane look promising although further catalyst improvement is required. Acetic acid from ethane and acrylonitrile from propane have a certain potential as an alternative to present technology. The outlook for acrolein and acrylic acid from propane is less favourable; new concepts for catalyst design are necessary. (orig.)

  13. On the catalytic gas phase oxidation of butadiene to furan

    Energy Technology Data Exchange (ETDEWEB)

    Kubias, B.; Rodemerck, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Ritschl, F.; Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie

    1998-12-31

    Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)

  14. Coupling catalytic hydrolysis and oxidation of HCN over HZSM-5 modified by metal (Fe,Cu) oxides

    Science.gov (United States)

    Hu, Yanan; Liu, Jiangping; Cheng, Jinhuan; Wang, Langlang; Tao, Lei; Wang, Qi; Wang, Xueqian; Ning, Ping

    2018-01-01

    In this work, a series of metal oxides (Fe,Cu) modified HZSM-5 catalysts were synthesized by incipient-wetness impregnation method and then characterized by XRD, N2 adsorption-desorption, H2-TPR, NH3-TPD, UV-vis, FT-IR and XPS measurements. The catalytic hydrolysis and oxidation behaviors toward HCN were investigated. The results indicated that the Fe-Cu/HZSM-5 catalysts exhibited more excellent performence on coupling catalytic hydrolysis and oxidation of HCN than HZSM-5, Fe/HZSM-5, Cu/HZSM-5, and both nearly 100% HCN conversion and 80% N2 selectivity were obtained at about 250 °C. The improved catalytic performance could be ascribed to the creation of highly dispersed iron and copper composites on the surface of the HZSM-5 support, the excellent redox and regulated acid properties of the active ingredients. Moreover, the highly N2 selectivity could be attributed to the good interaction between the Fe and Cu nanocomposites which was facilitated to the NH3-SCR (selective catalytic reduction of NO by NH3) reaction.

  15. Catalytic oxidation and spectroscopic analysis of simulated wastewater containing acid chrome blue K by using chlorine dioxide as oxidant.

    Science.gov (United States)

    Yu, Fengjun; Shi, Laishun

    2010-01-01

    An activated carbon-MnO(2) catalyst was prepared by the dipping-calcination method using activated carbon as catalyst support. The catalyst was used for the catalytic oxidation of simulated acid chrome blue K wastewater. The COD removal efficiency and decolor efficiency by catalytic oxidation are 72.0% and 87.8%, respectively, at the condition of wastewater's COD is 2,418 mg/L, the optimum pH value is 1.2, the dosage of chlorine dioxide is 1,200 mg/L, the dosage of activated carbon-MnO(2) catalyst is 4 g by reacting 50 min. The COD removal efficiency by catalytic oxidation is great than that of chemical oxidation. The COD removal efficiency only decreased a little after the catalyst used 8 times. The FTIR spectra indicate that the active ingredient of manganese dioxide is linked with activated carbon by chemical bond, not merely mechanical blending. The intermediates during the degradation process were obtained by using online infrared spectrum analysis. The degradation reaction mechanism of acid chrome blue K by chlorine dioxide oxidation was proposed based upon the experiment evidence.

  16. Catalytic water oxidation by single-site ruthenium catalysts.

    Science.gov (United States)

    Concepcion, Javier J; Jurss, Jonah W; Norris, Michael R; Chen, Zuofeng; Templeton, Joseph L; Meyer, Thomas J

    2010-02-15

    A series of monomeric ruthenium polypyridyl complexes have been synthesized and characterized, and their performance as water oxidation catalysts has been evaluated. The diversity of ligand environments and how they influence rates and reaction thermodynamics create a platform for catalyst design with controllable reactivity based on ligand variations.

  17. Flame Synthesis of Composite Oxides for Catalytic Applications

    DEFF Research Database (Denmark)

    Jensen, Joakim Reimer

    2002-01-01

    . These investigations prove that synthesis in a premixed flame is a very attractive method for the preparation of high surface area spinel structures with a high degree of crystallinity and a good resistance against sintering. ZnAl2O4, CuAl2O4 and MgAl2O4 spinel structures have been synthesized. The CuAl2O4 spinel...... exhibits a high activity for alcohol dehydrogenation due to a high reduced copper surface area. The copper surface areas of the reduced copper catalysts are measured employing N2O-titration. Treating the reduced copper catalysts with N2O results in a mild oxidation and only the surface layer of the copper...... crystallites is oxidized. A number of complications may arise using the N2O-titration. It may be difficult to obtain full oxidation of the copper surface without having some oxidation of the bulk. Secondly, some sintering of the nano-sized copper crystallites may occur due to the exothermic nature...

  18. Study of nano-structured ceria for catalytic CO oxidation

    Czech Academy of Sciences Publication Activity Database

    Valechha, D.; Lokhande, S.; Klementová, Mariana; Šubrt, Jan; Rayalu, S.; Labhsetwar, N.

    2011-01-01

    Roč. 21, č. 11 (2011), s. 3718-3725 ISSN 0959-9428 Institutional research plan: CEZ:AV0Z40320502 Keywords : mesoporous CeO2 * titania * alumina * oxides Subject RIV: CA - Inorganic Chemistry Impact factor: 5.968, year: 2011

  19. Catalytic oxidation of benzene using DBD corona discharges

    International Nuclear Information System (INIS)

    Lu, B.; Zhang, X.; Yu, X.; Feng, T.; Yao, S.

    2006-01-01

    Plasma oxidation of benzene (C 6 H 6 ) in oxygen and nitrogen was investigated using a dielectric barrier discharge (DBD) reactor with or without MnO 2 or TiO 2 at atmospheric pressure and without external heating except plasma heating. An alternative current power supply was used to generate corona discharges for the plasma oxidation. The energy density was controlled under 200 J/L to keep an increase in gas temperature less than 167 K. C 6 H 6 was oxidized to carbon monoxide (CO) and dioxide (CO 2 ). Typically, the energy efficiency at an energy density of 92 J/L was about 0.052, 0.039, and 0.024 mol/kWh with MnO 2 , TiO 2 , and without MnO 2 and TiO 2 , respectively. Benzene oxidation mechanism was mentioned. A comparison on energy efficiency as a function of initial concentration of hydrocarbons, inorganic sulphur compounds, and chloro (fluoro and bromo) carbons was given

  20. Catalytic wet oxidative degradation of filter paper waste simulates

    International Nuclear Information System (INIS)

    Shatta, H.A.; Saleh, H.M.; Bayoumi, T.A.

    2005-01-01

    This study is part of a comprehensive research program carried out at Radioisotope Department, Atomic Energy Authority, Egypt, aiming at the treatment of organic wastes simulate to achieve acceptable weight and volume reduction. The process is based on the wet oxidative degradation of these wastes, at a laboratory scale, using hydrogen peroxide as oxidant at atmospheric pressure and at 100 degree C. The present study was concerned with the treatment of filter paper waste simulates, as one of organic wastes originating from the peaceful applications of the nuclear technology, in the presence of two types of catalysts namely; copper sulphate and ferrous sulphate. The main aim of this treatment is to achieve an acceptable weight and volume reduction. That waste was subjected to wet oxidative degradation process at atmospheric pressure and 100 degree C using 35% hydrogen peroxide as oxidant in the presence of different concentrations of ferrous sulphate or copper sulphate as catalysts. Elemental analysis and IR spectroscopy were performed for the solid residue and the secondary waste solution resulted from the treatment process to follow the degradation process. Increasing the concentration of catalyst was accompanied with an acceptable increase in the weight reduction and conversion percentages. Up to 95% total weight reduction was obtained in the case of using copper sulphate as catalyst. Also, through this technique, the organic portion of these wastes is converted to carbon dioxide and water and hence the remaining solution is considered as a form suitable for subsequent immobilization process

  1. A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

    DEFF Research Database (Denmark)

    1999-01-01

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

  2. A study on the reaction characteristics of vanadium-impregnated natural manganese oxide in ammonia selective catalytic reduction.

    Science.gov (United States)

    Kim, Sung Su; Lee, Sang Moon; Park, Kwang Hee; Kwon, Dong Wook; Hong, Sung Chang

    2011-05-01

    This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH3) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH3 oxidation at high temperatures. From the NH3 temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature.

  3. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    International Nuclear Information System (INIS)

    Das, Lalitendu; Xu, Siquan; Shi, Jian

    2017-01-01

    Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C 2 C 1 Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H 2 O 2 as oxidizing agent in a batch reactor. CoCl 2 and Nb 2 O 5 proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H 2 O 2 concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M w ) of liquid stream lignin after oxidation, for CoCl 2 and Nb 2 O 5 catalysts were 1,202 and 1,520 g mol −1 , respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

  4. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Das, Lalitendu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); Xu, Siquan [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); College of Chemical Engineering, Nanjing Forestry University, Nanjing (China); Shi, Jian, E-mail: j.shi@uky.edu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States)

    2017-08-10

    Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C{sub 2}C{sub 1}Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H{sub 2}O{sub 2} as oxidizing agent in a batch reactor. CoCl{sub 2} and Nb{sub 2}O{sub 5} proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H{sub 2}O{sub 2} concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M{sub w}) of liquid stream lignin after oxidation, for CoCl{sub 2} and Nb{sub 2}O{sub 5} catalysts were 1,202 and 1,520 g mol{sup −1}, respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

  5. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Lalitendu Das

    2017-08-01

    Full Text Available Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C2C1Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H2O2 as oxidizing agent in a batch reactor. CoCl2 and Nb2O5 proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H2O2 concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (Mw of liquid stream lignin after oxidation, for CoCl2 and Nb2O5 catalysts were 1,202 and 1,520 g mol−1, respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

  6. Catalytic Templating Approaches for Three-Dimensional Hollow Carbon/Graphene Oxide Nano-Architectures

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Gun-Hee; Shin, Yongsoon; Choi, Daiwon; Arey, Bruce W.; Exarhos, Gregory J.; Wang, Chong M.; Choi, Wonyong; Liu, Jun

    2013-01-01

    We report a catalytic templating method to synthesize well-controlled, three-dimensional (3D) nano-architectures with graphene oxide sheets. The 3D composites are prepared via self-assembly of carbon, GO, and spherical alumina-coated silica (ACS) templates during a catalytic reaction porcess. By changing the GO content, we can systematically tune the architecture from layered composites to 3D hollow structures to microporous materials. The composites show a synergistic effect with significantly superior properties than either pure carbon or r-GO prepared with a significant enhancement to its capacitance at high current density.

  7. 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.

  8. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei [South China Univ. of Technology, Guangzhou (China)

    2014-06-15

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS{sub 4})) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS{sub 4}). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS{sub 4})/H{sub 2}O{sub 2} was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS{sub 4})/H{sub 2}O{sub 2} system.

  9. Electrochemical study on the cationic promotion of the catalytic SO2 oxidation in pyrosulfate melts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cappeln, Frederik Vilhelm

    1998-01-01

    on the catalytic oxidation of SO2 in the V2O5-M2S2O7 system and the effect of these alkali cations on the electrochemical behavior of V2O5 in the alkali pyrosulfate melts It has been shown that Na+ ions had a promoting effect on the V(V) reversible arrow V(IV) electrochemical reaction. Sodium ions accelerate both...... in the catalytic SO, oxidation most likely is the oxidation of V(IV) to V(V) and the Na+ and Cs+ promoting effect is based on the acceleration of this stage. It has also been proposed that voltammetric measurements can be used for fast optimization of the composition of the vanadium catalyst (which...

  10. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress*♦

    Science.gov (United States)

    Benoit, Stéphane L.; Maier, Robert J.

    2016-01-01

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H2O2). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains (katAH56A and katAY339A) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H2O2-dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. PMID:27605666

  11. 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.

  12. Synthesis, characterization and catalytic activity toward methanol oxidation of electrocatalyst Pt4+-NH2-MCM-41

    International Nuclear Information System (INIS)

    Zheng Huajun; Chen Zuo; Wang Limin; Ma Chun’an

    2012-01-01

    Highlights: ► It was first confirmed that the Pt 4+ exhibited a good electro-catalytic property for methanol oxidation. ► The Pt 4+ perfectly distributed on a mesoporous molecular sieve matrix synthesis by a facile method. ► The good performance of catalyst resistance to poisoning because of a homogeneous distribution of Pt 4+ and large specific surface area. - Abstract: Mesoporous material with functional group (Pt 4+ -NH 2 -MCM-41) was prepared by grafting aminopropyl group and adsorbing platinum ions on the surface of the commercial molecular sieve (MCM-41). The characterization carried out by X-ray photoelectron spectroscopy, X-ray diffraction, and N 2 adsorption–desorption measurement pointed out that Pt was adsorbed on the NH 2 -MCM-41 surface as the oxidation state (Pt 4+ ) and the surface area of Pt 4+ -NH 2 -MCM-41 was up to 564 m 2 /g. Transmission electron microscopy and elemental mapping indicated a homogeneous distribution of Pt 4+ throughout all surface of the mesoporous materials. Electro-catalytic properties of methanol oxidation on the Pt 4+ -NH 2 -MCM-41 electrode were investigated with electrochemical methods. The results showed that the Pt 4+ -NH 2 -MCM-41 electrode exhibited catalytic activity in the methanol electro-oxidation with the apparent activation energy being 49.29 kJ/mol, and the control step of methanol electro-oxidation was the mass transfer process. It is first proved that platinum ions had good electro-catalytic property for methanol oxidation and provided a new idea for developing electrode materials in future.

  13. Mn-Ce-V-WOx/TiO2 SCR Catalysts: Catalytic Activity, Stability and Interaction among Catalytic Oxides

    Directory of Open Access Journals (Sweden)

    Xuteng Zhao

    2018-02-01

    Full Text Available A series of Mn-Ce-V-WOx/TiO2 composite oxide catalysts with different molar ratios (active components/TiO2 = 0.1, 0.2, 0.3, 0.6 have been prepared by wet impregnation method and tested in selective catalytic reduction (SCR of NO by NH3 in a wide temperature range. These catalysts were also characterized by X-ray diffraction (XRD, Transmission Electron Microscope (TEM, in situ Fourier Transform infrared spectroscopy (in situ FTIR, H2-Temperature programmed reduction (H2-TPR and X-ray photoelectron spectroscopy (XPS. The results show the catalyst with a molar ratio of active components/TiO2 = 0.2 exhibits highest NO conversion value between 150 °C to 400 °C and good resistance to H2O and SO2 at 250 °C with a gas hourly space velocity (GHSV value of 40,000 h−1. Different oxides are well dispersed and interact with each other. NH3 and NO are strongly adsorbed on the catalyst surface and the adsorption of the reactant gas leads to a redox cycle with the valence state change among the surface oxides. The adsorption of SO2 on Mn4+ and Ce4+ results in good H2O and SO2 resistance of the catalyst, but the effect of Mn and Ce are more than superior water and sulfur resistance. The diversity of valence states of the four active components and their high oxidation-reduction performance are the main reasons for the high NO conversion in this system.

  14. Removal of formaldehyde over Mn(x)Ce(1)-(x)O(2) catalysts: thermal catalytic oxidation versus ozone catalytic oxidation.

    Science.gov (United States)

    Li, Jia Wei; Pan, Kuan Lun; Yu, Sheng Jen; Yan, Shaw Yi; Chang, Moo Been

    2014-12-01

    Mn(x)Ce(1)-(x)O(2) (x: 0.3-0.9) prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde (HCHO). At x=0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of CeO(2) to form a solid solution. The catalytic activity was best at x=0.5, at which the temperature of 100% removal rate is the lowest (270°C). The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5wt.% CuO(x) into Mn(0.5)Ce(0.5)O(2). With ozone catalytic oxidation, HCHO (61 ppm) in gas stream was completely oxidized by adding 506 ppm O₃over Mn(0.5)Ce(0.5)O(2) catalyst with a GHSV (gas hourly space velocity) of 10,000 hr⁻¹ at 25°C. The effect of the molar ratio of O(3) to HCHO was also investigated. As O(3)/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O(3)/HCHO ratio of 8, the mineralization efficiency of HCHO to CO(2) was 86.1%. At 25°C, the p-type oxide semiconductor (Mn(0.5)Ce(0.5)O(2)) exhibited an excellent ozone decomposition efficiency of 99.2%, which significantly exceeded that of n-type oxide semiconductors such as TiO(2), which had a low ozone decomposition efficiency (9.81%). At a GHSV of 10,000 hr⁻¹, [O(3)]/[HCHO]=3 and temperature of 25°C, a high HCHO removal efficiency (≥ 81.2%) was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal. Copyright © 2014. Published by Elsevier B.V.

  15. Removal of nitrogen compounds from gasification gas by selective catalytic or non-catalytic oxidation; Typpiyhdisteiden poisto kaasutuskaasusta selektiivisellae katalyyttisellae ja ei-katalyyttisellae hapetuksella

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-01

    In gasification reactive nitrogenous compounds are formed from fuel nitrogen, which may form nitrogen oxides in gas combustion. In fluidized bed gasification the most important nitrogenous compound is ammonia (NH{sub 3}). If ammonia could be decomposed to N{sub 2} already before combustion, the emissions if nitrogen oxides could be reduced significantly. One way of increasing the decomposition rate of NH{sub 3} could be the addition of suitable reactants to the gas, which would react with NH{sub 3} and produce N{sub 2}. The aim of this research is to create basic information, which can be used to develop a new method for removal of nitrogen compounds from gasification gas. The reactions of nitrogen compounds and added reactants are studied in reductive atmosphere in order to find conditions, in which nitrogen compounds can be oxidized selectively to N{sub 2}. The project consists of following subtasks: (1) Selective non-catalytic oxidation (SNCO): Reactions of nitrogen compounds and oxidizers in the gas phase, (2) Selective catalytic oxidation (SCO): Reactions of nitrogen compounds and oxidizers on catalytically active surfaces, (3) Kinetic modelling of experimental results in co-operation with the Combustion Chemistry Research Group of Aabo Akademi University. The most important finding has been that NH{sub 3} can be made to react selectively with the oxidizers even in the presence of large amounts of CO and H{sub 2}. Aluminium oxides were found to be the most effective materials promoting selectivity. (author)

  16. Study of the catalytic activity of mixed non-stoichiometric uranium-thorium oxides in carbon monoxide oxidation

    International Nuclear Information System (INIS)

    Brau, G.

    1969-06-01

    The aim of this work has been to study the catalytic properties of non-stoichiometric uranium-thorium oxides having the general formula U x Th 1-x O 2+y , for the oxidation of carbon monoxide. The preparation of pure, homogeneous, isotropic solids having good structural stability and a surface area as high as possible calls for a strict control of the conditions of preparation of these oxides right from the preparation of 'mother salts': the mixed oxalates U x Th 1-x (C 2 O 4 ) 2 , 2H 2 O. A study has been made of their physico-chemical properties (overall and surface chemical constitution, texture, structure, electrical conductivity), as well as of their adsorption properties with respect to gaseous species occurring in the catalytic reaction. This analysis has made it possible to put forward a reaction mechanism based on successive oxidations and reductions of the active surface by the reactants. A study of the reactions kinetics has confirmed the existence of this oxidation-reduction mechanism which only occurs for oxides having a uranium content of above 0.0014. The carbon dioxide produced by the reaction acts as an inhibitor by blocking the sites on which carbon monoxide can be adsorbed. These non-stoichiometric mixed oxides are a particularly clear example of catalysis by oxygen exchange between the solid and the gas phase. (author) [fr

  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 Oxidation of Lignins into the Aromatic Aldehydes: General Process Trends and Development Prospects

    Directory of Open Access Journals (Sweden)

    Valery E. Tarabanko

    2017-11-01

    Full Text Available This review discusses principal patterns that govern the processes of lignins’ catalytic oxidation into vanillin (3-methoxy-4-hydroxybenzaldehyde and syringaldehyde (3,5-dimethoxy-4-hydroxybenzaldehyde. It examines the influence of lignin and oxidant nature, temperature, mass transfer, and of other factors on the yield of the aldehydes and the process selectivity. The review reveals that properly organized processes of catalytic oxidation of various lignins are only insignificantly (10–15% inferior to oxidation by nitrobenzene in terms of yield and selectivity in vanillin and syringaldehyde. Very high consumption of oxygen (and consequentially, of alkali in the process—over 10 mol per mol of obtained vanillin—is highlighted as an unresolved and unexplored problem: scientific literature reveals almost no studies devoted to the possibilities of decreasing the consumption of oxygen and alkali. Different hypotheses about the mechanism of lignin oxidation into the aromatic aldehydes are discussed, and the mechanism comprising the steps of single-electron oxidation of phenolate anions, and ending with retroaldol reaction of a substituted coniferyl aldehyde was pointed out as the most convincing one. The possibility and development prospects of single-stage oxidative processing of wood into the aromatic aldehydes and cellulose are analyzed.

  19. Dehydrogenase-Catalyzed Oxidation of Furanics: Exploitation of Hemoglobin Catalytic Promiscuity.

    Science.gov (United States)

    Jia, Hao-Yu; Zong, Min-Hua; Yu, Hui-Lei; Li, Ning

    2017-09-22

    The catalytic promiscuity of hemoglobin (Hb) was explored for regenerating oxidized nicotinamide cofactors [NAD(P) + ]. With H 2 O 2 as oxidant, Hb efficiently oxidized NAD(P)H into NAD(P) + within 30 min. The new NAD(P) + regeneration system was coupled with horse liver alcohol dehydrogenase (HLADH) for the oxidation of bio-based furanics such as furfural and 5-hydroxymethylfurfural (HMF). The target acids (e.g., 2,5-furandicarboxylic acid, FDCA) were prepared with moderate-to-good yields. The enzymatic regeneration method was applied in l-glutamic dehydrogenase (DH)-mediated oxidative deamination of lglutamate and for l-lactic-DH-mediated oxidation of l-lactate, which furnished α-ketoglutarate and pyruvate in yields of 97 % and 81 %, respectively. A total turnover number (TTON) of up to approximately 5000 for cofactor and an E factor of less than 110 were obtained in the bi-enzymatic cascade synthesis of α-ketoglutarate. Overall, a proof-of-concept based on catalytic promiscuity of Hb was provided for in situ regeneration of NAD(P) + in DH-catalyzed oxidation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

    International Nuclear Information System (INIS)

    Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

    2014-01-01

    This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

  1. Nanodiamond-Gold Nanocomposites with the Peroxidase-Like Oxidative Catalytic Activity.

    Science.gov (United States)

    Kim, Min-Chul; Lee, Dukhee; Jeong, Seong Hoon; Lee, Sang-Yup; Kang, Eunah

    2016-12-21

    Novel nanodiamond-gold nanocomposites (NDAus) are prepared, and their oxidative catalytic activity is examined. Gold nanoparticles are deposited on carboxylated nanodiamonds (NDs) by in situ chemical reduction of gold precursor ions to produce NDAus, which exhibit catalytic activity for the oxidation of o-phenylenediamine in the presence of hydrogen peroxide similarly to a peroxidase. This remarkable catalytic activity is exhibited only by the gold nanoparticle-decorated NDs and is not observed for either Au nanoparticles or NDs separately. Kinetic oxidative catalysis studies show that NDAus exhibit a ping-pong mechanism with an activation energy of 93.3 kJ mol -1 , with the oxidation reaction rate being proportional to the substrate concentration. NDAus retain considerable activity even after several instances of reuse and are compatible with a natural enzyme, allowing the detection of xanthine using cascade catalysis. Association with gold nanoparticles makes NDs a good carbonic catalyst due to charge transfer at the metal-carbon interface and facilitated substrate adsorption. The results of this study suggest that diverse carbonic catalysts can be obtained by interfacial incorporation of various metal/inorganic substances.

  2. Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

    KAUST Repository

    Zhang, Tao

    2011-11-01

    The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

  3. I.C. Engine emission reduction by copper oxide catalytic converter

    Science.gov (United States)

    Venkatesan, S. P.; Shubham Uday, Desai; Karan Hemant, Borana; Rajarshi Kushwanth Goud, Kagita; Lakshmana Kumar, G.; Pavan Kumar, K.

    2017-05-01

    The toxic gases emitted from diesel engines are more than petrol engines. Predicting the use of diesel engines, even more in future, this system is developed and can be used to minimize the harmful gases. Toxic gases include NOX, CO, HC and Smoke which are harmful to the atmosphere as well as to the human beings. The main aim of this work is to fabricate system, where the level of intensity of toxic gases is controlled through chemical reaction to more agreeable level. This system acts itself as an exhaust system; hence there is no needs to fit separate the silencer. The whole assembly is fitted in the exhaust pipe from engine. In this work, catalytic converter with copper oxide as a catalyst, by replacing noble catalysts such as platinum, palladium and rhodium is fabricated and fitted in the engine exhaust. With and without catalytic converter, the experimentations are carried out at different loads such as 0%, 25%, 50%, 75%, and 100% of maximum rated load. From the experimental results it is found that the maximum reduction is 32%, 61% and 21% for HC, NOx and CO respectively at 100% of maximum rated load when compared to that of without catalytic converter. This catalytic converter system is cash effective and more economical than the existing catalytic converter.

  4. Partial oxidation of methane by pulsed corona discharges

    Science.gov (United States)

    Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

    2014-09-01

    Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

  5. Studies on the Catalytic Properties of Partially Purified Alkaline Proteases from Some Selected Microorganisms

    Directory of Open Access Journals (Sweden)

    Titilayo Olufunke Femi-Ola

    2012-09-01

    Full Text Available Aims: The research was done to study the conditions enhancing catalytic activities of alkaline proteases from Vibro sp., Lactobacillus brevis, Zymomonas sp., Athrobacter sp., Corynebacterium sp. and Bacillus subtilis.Methodology and Results: The proteolytic enzymes were purified in 2-step procedures involving ammonium sulphate precipitation and sephadex G-150 gel permeation chromatography. The upper and lower limits for the specific activities of proteases from the selected microorganisms were estimated at 20.63 and 47.51 units/mg protein with Zymomonas protease having the highest specific activity towards casein as its substrate and purification fold of 3.46, while that ofLactobacillus brevis protease was 8.06. The native molecular weights of these active proteins ranged from 30.4 to 45.7 kDa with Athrobacter sp. protease having the highest weight for its subunits. The proteolytic enzymes had optimum pH range of 8 to 10 and temperature range of 50 to 62 ºC accounting for the percentage relative activity range of 75 to 94% and 71 to 84 % respectively. The activities of Lactobacillus brevis and Bacillus subtilis proteases were maximum at pH 9 and 10 respectively. Lactobacillus brevis protease activity was maximum at temperature of 62 ºC, while beyond this value, a general thermal instability of these active proteins was observed. At above 70 ºC, the catalytic activities of Corynebacterium sp., Vibrio sp., Zymomonas sp. and Arthrobacter sp. proteases were progressively reduced over a period of 120 min of incubation, while Bacillus subtlis and Lactobacillus brevis proteases were relatively stable. Effect of metal ions was investigated on the catalytic activity of protease from the microorganisms. Lactobacillus brevis,Zymomonas sp., Arthrobacter sp., Corynebacterium sp. and Bacillus subtilis protease activities were strongly activated by metal ions such as Ca+2 and Mg+2. Enzyme activities were inhibited strongly by Cu2+ and Hg2+ but were not

  6. Air trichloroethylene oxidation in a corona plasma-catalytic reactor

    Science.gov (United States)

    Masoomi-Godarzi, S.; Ranji-Burachaloo, H.; Khodadadi, A. A.; Vesali-Naseh, M.; Mortazavi, Y.

    2014-08-01

    The oxidative decomposition of trichloroethylene (TCE; 300 ppm) by non-thermal corona plasma was investigated in dry air at atmospheric pressure and room temperature, both in the absence and presence of catalysts including MnOx, CoOx. The catalysts were synthesized by a co-precipitation method. The morphology and structure of the catalysts were characterized by BET surface area measurement and Fourier Transform Infrared (FTIR) methods. Decomposition of TCE and distribution of products were evaluated by a gas chromatograph (GC) and an FTIR. In the absence of the catalyst, TCE removal is increased with increases in the applied voltage and current intensity. Higher TCE removal and CO2 selectivity is observed in presence of the corona and catalysts, as compared to those with the plasma alone. The results show that MnOx and CoOx catalysts can dissociate the in-plasma produced ozone to oxygen radicals, which enhances the TCE decomposition.

  7. Method for improving catalyst function in auto-thermal and partial oxidation reformer-based processors

    Science.gov (United States)

    Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H.D.; Ahluwalia, Rajesh K.

    2014-08-26

    The invention provides a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

  8. Gold & silver nanoparticles supported on manganese oxide: Synthesis, characterization and catalytic studies for selective oxidation of benzyl alcohol

    Directory of Open Access Journals (Sweden)

    Saad Alabbad

    2014-12-01

    Full Text Available Nano-gold and silver particles supported on manganese oxide were synthesized by the co-precipitation method. The catalytic properties of these materials were investigated for the oxidation of benzyl alcohol using molecular oxygen as a source of oxygen. The catalyst was calcined at 300, 400 and 500 °C. They were characterized by electron microscopy, powder X-ray diffraction (XRD and surface area. It was observed that the calcination temperature affects the size of the nanoparticle, which plays a significant role in the catalytic process. The catalyst calcined at 400 °C, gave a 100% conversion and >99% selectivity, whereas catalysts calcined at 300 and 500 °C gave a conversion of 69.51% and 19.90% respectively, although the selectivity remains >99%.

  9. Process for forming a homogeneous oxide solid phase of catalytically active material

    Science.gov (United States)

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  10. 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...

  11. Influence of Rare Earth Doping on the Structural and Catalytic Properties of Nanostructured Tin Oxide

    Directory of Open Access Journals (Sweden)

    Maciel Adeilton

    2008-01-01

    Full Text Available AbstractNanoparticles of tin oxide, doped with Ce and Y, were prepared using the polymeric precursor method. The structural variations of the tin oxide nanoparticles were characterized by means of nitrogen physisorption, carbon dioxide chemisorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The synthesized samples, undoped and doped with the rare earths, were used to promote the ethanol steam reforming reaction. The SnO2-based nanoparticles were shown to be active catalysts for the ethanol steam reforming. The surface properties, such as surface area, basicity/base strength distribution, and catalytic activity/selectivity, were influenced by the rare earth doping of SnO2and also by the annealing temperatures. Doping led to chemical and micro-structural variations at the surface of the SnO2particles. Changes in the catalytic properties of the samples, such as selectivity toward ethylene, may be ascribed to different dopings and annealing temperatures.

  12. Catalytic oxidation for treatment of ECLSS and PMMS waste streams. [Process Material Management Systems

    Science.gov (United States)

    Akse, James R.; Thompson, John; Scott, Bryan; Jolly, Clifford; Carter, Donald L.

    1992-01-01

    Catalytic oxidation was added to the baseline multifiltration technology for use on the Space Station Freedom in order to convert low-molecular weight organic waste components such as alcohols, aldehydes, ketones, amides, and thiocarbamides to CO2 at low temperature (121 C), thereby reducing the total organic carbon (TOC) to below 500 ppb. The rate of reaction for the catalytic oxidation of aqueous organics to CO2 and water depends primarily upon the catalyst, temperature, and concentration of reactants. This paper describes a kinetic study conducted to determine the impact of each of these parameters upon the reaction rate. The results indicate that a classic kinetic model, the Langmuir-Hinshelwood rate equation for heterogeneous catalysis, can accurately represent the functional dependencies of this rate.

  13. Partial Photochemical Oxidation Was a Dominant Fate of Deepwater Horizon Surface Oil.

    Science.gov (United States)

    Ward, Collin P; Sharpless, Charles M; Valentine, David L; French-McCay, Deborah P; Aeppli, Christoph; White, Helen K; Rodgers, Ryan P; Gosselin, Kelsey M; Nelson, Robert K; Reddy, Christopher M

    2018-02-20

    Following the Deepwater Horizon (DWH) blowout in 2010, oil floated on the Gulf of Mexico for over 100 days. In the aftermath of the blowout, substantial accumulation of partially oxidized surface oil was reported, but the pathways that formed these oxidized residues are poorly constrained. Here we provide five quantitative lines of evidence demonstrating that oxidation by sunlight largely accounts for the partially oxidized surface oil. First, residence time on the sunlit sea surface, where photochemical reactions occur, was the strongest predictor of partial oxidation. Second, two-thirds of the partial oxidation from 2010 to 2016 occurred in less than 10 days on the sunlit sea surface, prior to coastal deposition. Third, multiple diagnostic biodegradation indices, including octadecane to phytane, suggest that partial oxidation of oil on the sunlit sea surface was largely driven by an abiotic process. Fourth, in the laboratory, the dominant photochemical oxidation pathway of DWH oil was partial oxidation to oxygenated residues rather than complete oxidation to CO 2 . Fifth, estimates of partial photo-oxidation calculated with photochemical rate modeling overlap with observed oxidation. We suggest that photo-oxidation of surface oil has fundamental implications for the response approach, damage assessment, and ecosystem restoration in the aftermath of an oil spill, and that oil fate models for the DWH spill should be modified to accurately reflect the role of sunlight.

  14. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    Science.gov (United States)

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  15. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    Science.gov (United States)

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Reaction kinetics of waste sulfuric acid using H2O2catalytic oxidation.

    Science.gov (United States)

    Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng

    2016-12-01

    The process of recovering waste sulfuric acids using H 2 O 2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H 2 O 2 , and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H 2 O 2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H 2 O 2 feeding rate of 50 g (kg waste acid) -1 per hour, and catalyst dosage of 0.2 wt% (waste acid weight), the removal efficiencies of COD and chrominance were both more than 99%, the recovery ratio of sulfuric acid was more than 95%, and the utilization ratio of H 2 O 2 was 88.57%. Waste sulfuric acid is a big environmental problem in China. The amount of waste sulfuric acid is huge every year. Many small and medium-sized businesses produced lots of waste acids, but they don't have an appropriate method to treat and recover them. H 2 O 2 catalytic oxidation has been used to treat and recover waste sulfuric acid and activated carbon is the catalyst here. Main parameters, such as temperature, feed rate of H 2 O 2 , and catalyst dosage, have been investigated. The reaction kinetics are discussed. This method can be economical and feasible for most small and medium-sized businesses.

  17. The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation

    Science.gov (United States)

    Hou, Jingtao; Li, Yuanzhi; Mao, Mingyang; Zhao, Xiujian; Yue, Yuanzheng

    2014-11-01

    The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel and facile strategy of synthesizing these unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework by hydrothermal redox reaction between Ce(NO3)3 and KMnO4 with KMnO4/Ce(NO3)3 at a molar ratio of 3 : 1 at 120 °C. Compared to pure OMS-2, the produced catalyst of Ce ion substituted OMS-2 ultrathin nanorods exhibits an enormous enhancement in the catalytic activity for benzene oxidation, which is evidenced by a significant decrease (ΔT50 = 100 °C, ΔT90 = 129 °C) in the reaction temperature of T50 and T90 (corresponding to the benzene conversion = 50% and 90%), which is considerably more efficient than the expensive supported noble metal catalyst (Pt/Al2O3). We combine both theoretical and experimental evidence to provide a new physical insight into the significant effect due to the defects induced by the Ce ion substitution on the catalytic activity of OMS-2. The formation of unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework leads to a significant enhancement of the lattice oxygen activity, thus tremendously increasing the catalytic activity.The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel

  18. Advances in reforming and partial oxidation of hydrocarbons for hydrogen production and fuel cell applications

    OpenAIRE

    Sengodan, Sivaprakash; Lan, Rong; Humphreys, John; Du, Dongwei; Xu, Wei; Wang, Huanting; Tao, Shanwen

    2017-01-01

    One of the most attractive routes for the production of hydrogen or syngas for use in fuel cell applications is the reforming and partial oxidation of hydrocarbons. The use of hydrocarbons in high temperature fuel cells is achieved through either external or internal reforming. Reforming and partial oxidation catalysis to convert hydrocarbons to hydrogen rich syngas plays an important role in fuel processing technology. The current research in the area of reforming and partial oxidation of me...

  19. Influence of Partial Neutralization on Catalytic Activity of Ion Exchange Resin

    Czech Academy of Sciences Publication Activity Database

    Holub, Ladislav; Jeřábek, Karel

    2005-01-01

    Roč. 231, 1-2 (2005), s. 21-26 ISSN 1381-1169 R&D Projects: GA ČR(CZ) GA104/02/1104 Institutional research plan: CEZ:AV0Z40720504 Keywords : catalysis * partial neutralization * polymer supports Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.348, year: 2005

  20. A study of the effect of gamma radiation and doping on the catalytic activity of some oxides in the decomposition of hydrogen per-oxide

    International Nuclear Information System (INIS)

    Mousa, M.A.

    1987-01-01

    The rates of hydrogen peroxide decomposition on pure, doped and gamma-irradiated oxides Chromium oxide, Cobalt oxide, Magnesium oxide Nickel oxide, Ferric oxide, Magnesium ferri oxide were measured in a temperature range of 25-40 degree centigrade. It was found that lattice defect induced by doping and gamma-irradiation affect the catalytic properties of the oxides, either by activation or deactivation. The correlation between the catalytic activity for the hydrogen peroxide decomposition and the electronic defects produced by doping and by gamma-irradiation in the oxides is dicussed. Generally, it was found that the p-type semiconductor oxides are more active towards hydrogen peroxide decomposition than the n-type semiconductor oxides. (orig./A.B.)

  1. Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sui, Minghao, E-mail: suiminghao.sui@gmail.com [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China); Xing, Sichu; Sheng, Li; Huang, Shuhang; Guo, Hongguang [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Ciprofloxacin in water was degraded by heterogeneous catalytic ozonation. Black-Right-Pointing-Pointer MnOx were supported on MWCNTs to serve as catalyst for ozonation. Black-Right-Pointing-Pointer MnOx/MWCNT exhibited highly catalytic activity on ozonation of ciprofloxacin in water. Black-Right-Pointing-Pointer MnOx/MWCNT resulted in effective antibacterial activity inhibition on ciprofloxacin. Black-Right-Pointing-Pointer MnOx/MWCNT promoted the generation of hydroxyl radicals. - Abstract: Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO{center_dot}) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide-OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on

  2. Helicobacter Catalase Devoid of Catalytic Activity Protects the Bacterium against Oxidative Stress.

    Science.gov (United States)

    Benoit, Stéphane L; Maier, Robert J

    2016-11-04

    Catalase, a conserved and abundant enzyme found in all domains of life, dissipates the oxidant hydrogen peroxide (H 2 O 2 ). The gastric pathogen Helicobacter pylori undergoes host-mediated oxidant stress exposure, and its catalase contains oxidizable methionine (Met) residues. We hypothesized catalase may play a large stress-combating role independent of its classical catalytic one, namely quenching harmful oxidants through its recyclable Met residues, resulting in oxidant protection to the bacterium. Two Helicobacter mutant strains ( katA H56A and katA Y339A ) containing catalase without enzyme activity but that retain all Met residues were created. These strains were much more resistant to oxidants than a catalase-deletion mutant strain. The quenching ability of the altered versions was shown, whereby oxidant-stressed (HOCl-exposed) Helicobacter retained viability even upon extracellular addition of the inactive versions of catalase, in contrast to cells receiving HOCl alone. The importance of the methionine-mediated quenching to the pathogen residing in the oxidant-rich gastric mucus was studied. In contrast to a catalase-null strain, both site-change mutants proficiently colonized the murine gastric mucosa, suggesting that the amino acid composition-dependent oxidant-quenching role of catalase is more important than the well described H 2 O 2 -dissipating catalytic role. Over 100 years after the discovery of catalase, these findings reveal a new non-enzymatic protective mechanism of action for the ubiquitous enzyme. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  3. Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Wael Ahmed Abou Taleb Sayed

    2011-01-13

    This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

  4. Effect of Au Precursor and Support on the Catalytic Activity of the Nano-Au-Catalysts for Propane Complete Oxidation

    Directory of Open Access Journals (Sweden)

    Arshid M. Ali

    2015-01-01

    Full Text Available Catalytic activity of nano-Au-catalyst(s for the complete propane oxidation was investigated. The results showed that the nature of both Au precursor and support strongly influences catalytic activity of the Au-catalyst(s for the propane oxidation. Oxidation state, size, and dispersion of Au nanoparticles in the Au-catalysts, surface area, crystallinity, phase structure, and redox property of the support are the key aspects for the complete propane oxidation. Among the studied Au-catalysts, the AuHAuCl4-Ce catalyst is found to be the most active catalyst.

  5. Metal and Metal Oxide Interactions and Their Catalytic Consequences for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Qingying; Ghoshal, Shraboni; Li, Jingkun; Liang, Wentao; Meng, Guangnan [ULVAC Technologies, Inc., 401; Che, Haiying [Shanghai; Zhang, Shiming [Shanghai; Ma, Zi-Feng [Shanghai; Mukerjee, Sanjeev

    2017-06-01

    Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nb in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt–Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt–O interactions improve the ORR activity by shortening the Pt–Pt bond distance. Pt donates electrons to NbOx in both Pt–Nb and Pt–O cases. The resultant electron efficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.

  6. Nanocarbon coating on the basis of partially reduced graphene oxide

    Science.gov (United States)

    Bocharov, G. S.; Budaev, V. P.; Eletskii, A. V.; Fedorovich, S. D.

    2017-11-01

    There has been developed an approach to the production of graphene as a result of the thermal reduction of graphene oxide (GO). GO has been synthesized by the use of the modified Hummers method with utilization of sodium nitrate and concentrated sulfuric acid. A paper-like material of 40 – 60 μm in thickness and 1.2 g/cm3 in density was formed on a filter after deposition from dispersion. The material was cut onto samples of about 15×25 mm2 in size which were experienced to the thermal treatment at various temperatures between 100 and 800 °C. This resulted in a set of GO samples reduced to various degrees. The degree of reduction was determined on the basis of measurements of the conductivity. Along with that the evolution of samples density was studied as the annealing temperature was enhanced. The analysis of the X-ray photoelectron spectra of partially reduced GO permitted the determination of the dynamics of changing the chemical composition of the material in the process of the thermal treatment. The analysis of Raman spectra of the GO samples indicates rather high degree of the disordering of the material. A possibility of the usage of the material produced as a nanocarbon coating in experiments on the interaction of high intense liquid flows with a wall surface is discussed.

  7. Synthesis and characterization of Cr-MSU-1 and its catalytic application for oxidation of styrene

    Science.gov (United States)

    Liu, Hong; Wang, Zhigang; Hu, Hongjiu; Liang, Yuguang; Wang, Mengyang

    2009-07-01

    Chromium-containing mesoporous silica material Cr-MSU-1 was synthesized using lauryl alcohol-polyoxyethylene (23) ether as templating agent under the neutral pH condition by two-step method. The sample was characterized by XRD, TEM, FT-IR, UV-Vis, ESR, ICP-AES and N 2 adsorption. Its catalytic performance for oxidation of styrene was studied. Effects of the solvent used, the styrene/H 2O 2 mole ratio and the reaction temperature and time on the oxidation of styrene over the Cr-MSU-1 catalyst were examined. The results indicate that Cr ions have been successfully incorporated into the framework of MSU-1 and the Cr-MSU-1 material has a uniform worm-like holes mesoporous structure. After Cr-MSU-1 is calcined, most of Cr 3+ is oxidized to Cr 5+ and Cr 6+ in tetrahedral coordination and no extra-framework Cr 2O 3 is formed. The Cr-MSU-1 catalyst is highly active for the selective oxidation of styrene and the main reaction products over Cr-MSU-1 are benzaldehyde and phenylacetaldehyde. Its catalytic performance remains stable within five repeated runs and no leaching is noticed for this chromium-based catalyst.

  8. Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene.

    Science.gov (United States)

    Lu, Hanfeng; Kong, Xianxian; Huang, Haifeng; Zhou, Ying; Chen, Yinfei

    2015-06-01

    Cu-Mn, Cu-Mn-Ce, and Cu-Ce mixed-oxide catalysts were prepared by a citric acid sol-gel method and then characterized by XRD, BET, H2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu-Mn-Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu-Mn-Ce catalyst, a portion of Cu and Mn species entered into the CeO2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu-Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu-Mn and Cu-Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species. Copyright © 2015. Published by Elsevier B.V.

  9. Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

    DEFF Research Database (Denmark)

    Hannemann, S.; Grunwaldt, Jan-Dierk; Kimmerle, B.

    2009-01-01

    The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on......-line mass spectrometry. This experimental strategy allowed collecting data on the structure of the noble metal (oxidation state) and the temperature along the catalyst bed. The reaction was investigated in a fixed-bed quartz microreactor (1-1.5 mm diameter) following the catalytic performance by on-line gas...... mass spectrometry (MS). Above the ignition temperature of the catalytic partial oxidation of methane (310-330 A degrees C), a zone with oxidized noble metals was observed in the inlet region of the catalyst bed, accompanied by a characteristic hot spot (over-temperature up to 150 A degrees C), while...

  10. Tailoring Catalytic Properties of Pd/Co₃O₄ Catalysts via Structure Engineering for Methane Oxidation.

    Science.gov (United States)

    Chen, Lufei; Zhu, Yan

    2018-04-01

    The catalytic behavior of Co3O4 catalysts loaded by Pd for methane oxidation can be tailored by distinct spatial architectures and surface structures of such catalysts. Pd nanoparticles nested in Co3O4 with hexagonal-like microflakes exhibited superior catalytic activity, that is, T10 = 250 °C and T90 = 325 °C are correlated to 10% and 90% conversion of methane. Further Pd/Co3O4 microflakes catalyst can almost restore to its initial value in the absence of water when water vapor was cut off. This excellent catalysis should be attributed to its exposed more open surface, more active oxygen species and stronger redox properties.

  11. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

    This work deals with the selective catalytic reduction of nitrogen oxides (NO x ), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N 2 , in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO 3 , on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  12. Preparation, photo-catalytic activity of cuprous oxide nano-crystallites with different sizes

    International Nuclear Information System (INIS)

    Tang Aidong; Xiao Yu; Ouyang Jing; Nie Sha

    2008-01-01

    Cuprous oxide (Cu 2 O) nano-crystallites with different sizes were prepared via electrolysis method and characterized by X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Its photo-catalytic activities in the degradation of methyl orange as the model pollutant using UV light as an energy source were investigated. The XRD patterns showed that the sizes of Cu 2 O nano-crystallite decreased with the increasement of cetyltrimethyl ammonium bromide (CTAB) being added into the electrolyte, which were ranging from 27 nm to 48 nm. The progress of photo-catalytic degradation of the methyl orange was observed by monitoring the concentration change of the methyl orange solution. The highest decolorization ratio of 90% was observed for the sample prepared by addition of 0.05 g/L CTAB after photo-degradating 50 mg/L of methyl orange solution for 70 min. The mechanism of photo-degradation was discussed

  13. Investigation of catalytic oxidation of diamond by water vapor and carbon dioxide in the presence of alkali melts of some rare earth oxides

    International Nuclear Information System (INIS)

    Kulakova, I.I.; Rudenko, A.P.; Sulejmenova, A.S.; Tolstopyatova, A.A.

    1978-01-01

    The results of an investigation of the catalytic oxydation of diamond by carbon dioxide and water vapors at 906 deg C in the presence of melts of some rare earth oxides in potassium hydroxide are given. The ion La 3+ was shown to possess the most catalytic activity. The earlier proposed mechanisms of the diamond oxidation by CO 2 and H 2 O were corroborated. The ions of rare earth elements were found to accelerate the different stages of the process

  14. Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

    KAUST Repository

    Baker, L. Robert

    2011-08-18

    The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

  15. Degradation of phenylamine by catalytic wet air oxidation using metal catalysts with modified supports.

    Science.gov (United States)

    Torrellas, Silvia A; Escudero, Gabriel O; Rodriguez, Araceli R; Rodriguez, Juan G

    2015-01-01

    The effect of acid treatments with HCl and HNO3 on the surface area and surface chemistry of three granular activated carbons was studied. These supports were characterized and the hydrochloric acid treatment leads to the best activated carbon support (AC2-C). The catalytic behavior of Pt, Ru and Fe (1 wt.%) supported on granular activated carbon treated with HCl was tested in the phenylamine continuous catalytic wet air oxidation in a three-phase, high-pressure catalytic reactor over a range of reaction temperatures 130-170ºC and total pressure of 1.0-3.0 MPa at LHSV = 0.4-1 h(-1), whereas the phenylamine concentration range and the catalyst loading were 5-16 mol.m(-3) and 0.5-1.5 g, respectively. Activity as well as conversion varied as a function of the metal, the catalyst preparation method and operation conditions. Higher activities were obtained with Pt incorporated on hydrochloric acid -treated activated carbon by the ion exchange method. In steady state, approximately 98% phenylamine conversion, 77% of TOC and 94% of COD removal, was recorded at 150ºC, 11 mol m(-3) of phenylamine concentration and 1.5 g of catalyst, and the selectivity to non-organic compounds was 78%. Several reaction intermediaries were detected. A Langmuir-Hinshelwood model gave an excellent fit of the kinetic data of phenylamine continuous catalytic wet air oxidation over the catalysts of this work.

  16. Generation of synthesis gas by partial oxidation of natural gas in a gas turbine

    NARCIS (Netherlands)

    Cornelissen, R.; Tober, E.; Kok, Jacobus B.W.; van der Meer, Theodorus H.

    2006-01-01

    The application of partial oxidation in a gas turbine (PO-GT) in the production of synthesis gas for methanol production is explored. In PO-GT, methane is compressed, preheated, partial oxidized and expanded. For the methanol synthesis a 12% gain in thermal efficiency has been calculated for the

  17. Mixed conducting materials for partial oxidation of hydrocarbons

    Directory of Open Access Journals (Sweden)

    Frade, J. R.

    2004-06-01

    Full Text Available Thermodynamic calculations with additional conditions for the conservation of carbon and hydrogen were used to predict the gas composition obtained by partial oxidation of methane as a function of oxygen partial pressure and temperature; this was used to assess the stability and oxygen permeability requirements of mixed conducting membrane materials proposed for this purpose. A re-examination of known mixed conductors shows that most materials with highest permeability still fail to fulfil the requirements of stability under reducing conditions. Other materials possess sufficient stability but their oxygen permeability is insufficient. Different approaches were thus used to attempt to overcome those limitations, including changes in composition in the A and B site positions of ABO3 perovskites, and tests of materials with different structure types. Promising results were obtained mainly for some materials with perovskite or related K2NiF4-type structures. Limited stability of the most promising materials shows that one should rely mainly on kinetic limitations in the permeate side to protect the mixed conductor from severe reducing conditions.

    Se han usado cálculos termodinámicos con condiciones adicionales para la conservación del carbono e hidrógeno para predecir la composición del gas obtenido mediante la oxidación parcial del metano en función de la presión parcial de oxígeno y de la temperatura; esto se ha usado para asegurar los requerimientos de estabilidad y permeabilidad al oxígeno de los materiales conductores mixtos empleados como membrana para este propósito. Un nuevo exámen de los conductores mixtos conocidos muestra que la mayoría de los materiales con la mayor permeabilidad todavía fallan en el cumplimiento de los requerimientos de estabilidad bajo condiciones reductoras. Otros materiales poseen suficiente estabilidad, pero su permeabilidad al oxígeno es insuficiente. Por ello se han empleado diferentes

  18. Inhibition effects in the partial oxidation of cyclohexane on polymer supported Co(II catalysts

    Directory of Open Access Journals (Sweden)

    MAJA ODOVIC

    2005-02-01

    Full Text Available Polymer supported catalysts with different contents of metal ions where synthesized by wet impregnation of the degassed support from ethanolic solutions of cobalt(II nitrate. Amacroreticular copolymer of poly-4-vinylpyridine with divinylbenzene was used as the support. The prepared catalysts were tested in the partial oxidation of cyclohexane to cyclohexanol and cyclohexanone. Activity tests were performed in a stainless steel, laboratory scale, stirred autoclave, in the semi batch regime under isothermal and non-isothermal conditions. Isothermal experiments where performed at 170 °C for 120 min. In the non-isothermal conditions. isothermal experiments where performed at 170 °C for 120 min. In the non-isothermal experiments, a constant heating rate of 0.3 degree/min was used in the range between 110 °C and 170 °C. Non-linear, least-squares analysis with the simplex optimization method and numerical simulation of the reaction model in each iterative step was used for the kinetic characterization of the process in a non-stationary, semi-batch regime. Apparent rate constants were obtained as an invariant measure of the catalytic system. Anon-linear effect of the content of metal ions on the reaction rate and on the ratio of the yield of the products was observed, which is attributed to a complex interactions between the reaction medium and the heterogeneous catalyst, including a catalyst-inhibition effect.

  19. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    Energy Technology Data Exchange (ETDEWEB)

    Pura, Jarosław, E-mail: jaroslawpura@gmail.com [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Laskowski, Zbigniew; Gierej, Maciej [Precious Metal Mint, Weteranów 95, 05-250 Radzymin (Poland)

    2016-12-01

    Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800–900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic “cauliflower-shape protrusions”. The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires’ surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires’ preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better

  20. Autothermal and partial oxidation reformer-based fuel processor, method for improving catalyst function in autothermal and partial oxidation reformer-based processors

    Science.gov (United States)

    Ahmed, Shabbir; Papadias, Dionissios D.; Lee, Sheldon H. D.; Ahluwalia, Rajesh K.

    2013-01-08

    The invention provides a fuel processor comprising a linear flow structure having an upstream portion and a downstream portion; a first catalyst supported at the upstream portion; and a second catalyst supported at the downstream portion, wherein the first catalyst is in fluid communication with the second catalyst. Also provided is a method for reforming fuel, the method comprising contacting the fuel to an oxidation catalyst so as to partially oxidize the fuel and generate heat; warming incoming fuel with the heat while simultaneously warming a reforming catalyst with the heat; and reacting the partially oxidized fuel with steam using the reforming catalyst.

  1. Plasma spray deposition of Al-Al2O3 coatings doped with metal oxides: catalytic applications

    International Nuclear Information System (INIS)

    Pranevicius, L.; Pranevicius, L.L.; Valatkevicius, P.; Valincius, V.

    2000-01-01

    Al-Al 2 O 3 (70% γ-phase) coatings 30-50 μm thick well-adhered to the steel sheets and with a highly developed surface area (100-120 m 2 g -1 ) were formed employing plasma-spray technology at atmospheric pressure in air. The plasma-gun with two sequential powder feeders was developed offering the ability to control particle trajectories through the plasma flame, and thus their thermal history. The Al powder is mainly melted and oxidized. Al(OH) 3 powder passes through the plasma torch with partial dissociation and is incorporated in the matrix of growing film with subsequent decomposition during thermal annealing at 560 C for 90 min. The good adhesion results are explained by the surface pre-treatment effects taking place on the periphery of the plasma torch moving along the surface of steel sheets. The plasma sprayed Al-Al 2 O 3 coatings doped with CuO and Cr 2 O 3 oxides showed characteristic catalytic combustion behaviors. (orig.)

  2. Catalytic oxidation of low-concentration CO at ambient temperature over supported Pd-Cu catalysts.

    Science.gov (United States)

    Wang, Fagen; Zhang, Haojie; He, Dannong

    2014-01-01

    The CO catalytic oxidation at ambient temperature and high space velocity was studied over the Pd-Cu/MOx (MOx = TiO2 and AI203) catalysts. The higher Brunauer-Emmett-Teller area surface of the A1203 support facilitates the dispersion of Pd2+ species, and the presence of Cu2Cl(OH)3 accelerates the re-oxidation of Pd0 to Pd2+ over the Pd-Cu/Al203 catalyst, which contributed to better performance of CO catalytic oxidation. The poorer activity of the Pd-Cu/TiO2 catalyst was attributed to the lower dispersion of Pd2+ species because of the less surface area and the non-formation of Cu2CI(OH)3 species. The presence of saturated moisture showed a negative effect on CO conversion over the two catalysts. This might be because of the competitive adsorption, the formation of carbonate species and the transformation of Cu2CI(OH)3 to inactive CuCI over the Pd-Cu/AI2O3 catalyst, which facilitates the aggregation of PdO species over the Pd-Cu/TiO2 catalyst under the moisture condition.

  3. Synergy Effects of the Mixture of Bismuth Molybdate Catalysts with SnO2/ZrO2/MgO in Selective Propene Oxidation and the Connection between Conductivity and Catalytic Activity

    DEFF Research Database (Denmark)

    Le, Minh Thang; Do, Van Hung; Truong, Duc Duc

    2016-01-01

    Bismuth molybdate catalysts have been used for partial oxidation and ammoxidation of light hydrocarbons since the 1950s. In particular, there is the synergy effect (the enhancement of the catalytic activity in the catalysts mixed from different components) in different phases of bismuth molybdate...... for the question: does the electrical conductivity influence the catalytic activity (which has been previously proposed by some authors). In this work, highly conductive materials (SnO2, ZrO2) and nonconductive materials (MgO) are added to beta bismuth molybdates (beta-Bi2Mo2O9) using mechanical mixing...... of these mixtures showed that the addition of 10% mol SnO2 to beta bismuth molybdate resulted in the highest activity while the addition of nonconductive MgO could not increase the catalytic activity. This shows that there may be a connection between conductivity and catalytic activity in the mixtures of bismuth...

  4. Development of a Catalytic Wet Air Oxidation Method to Produce Feedstock Gases from Waste Polymers

    Science.gov (United States)

    Kulis, Michael J.; Guerrero-Medina, Karen J.; Hepp, Aloysius F.

    2012-01-01

    Given the high cost of space launch, the repurposing of biological and plastic wastes to reduce the need for logistical support during long distance and long duration space missions has long been recognized as a high priority. Described in this paper are the preliminary efforts to develop a wet air oxidation system in order to produce fuels from waste polymers. Preliminary results of partial oxidation in near supercritical water conditions are presented. Inherent corrosion and salt precipitation are discussed as system design issues for a thorough assessment of a second generation wet air oxidation system. This work is currently being supported by the In-Situ Resource Utilization Project.

  5. 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.

  6. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  7. 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

  8. Composite of Au-Pd nanoalloys/reduced graphene oxide toward catalytic selective organic transformation to fine chemicals

    Science.gov (United States)

    Zhang, Yanhui; Gao, Fei; Fu, Ming-Lai

    2018-01-01

    A facile, stabilizing-molecules-free strategy has been utilized for anchoring Au-Pd alloy nanoparticles onto the flat surface of two-dimensional (2D) reduced graphene oxide (RGO) nanosheets. Formation of Au-Pd nanoalloys and loading onto the RGO are accomplished simultaneously. The Au-Pd/reduced graphene oxide (Au-Pd/RGO) exhibits higher catalytic activity than both Au/RGO and Pd/RGO, prepared by the same approach toward selective oxidation of benzyl alcohol and selective reduction of nitroaromatics, the catalytic activity order can be in good agreement with the noble metal particles size distribution of the Au, Pd and Au-Pd/RGO.

  9. Polymeric heterogeneous catalysts of transition-metal oxides: surface characterization, physicomechanical properties, and catalytic activity.

    Science.gov (United States)

    Nhi, Bui Dinh; Akhmadullin, Renat Maratovich; Akhmadullina, Alfiya Garipovna; Samuilov, Yakov Dmitrievich; Aghajanian, Svetlana Ivanova

    2013-12-16

    We investigate the physicomechanical properties of polymeric heterogeneous catalysts of transition-metal oxides, specifically, the specific surface area, elongation at break, breaking strength, specific electrical resistance, and volume resistivity. Digital microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive analysis are used to study the surfaces of the catalysts. The experimental results show that polymeric heterogeneous catalysts of transition-metal oxides exhibit high stability and can maintain their catalytic activity under extreme reaction conditions for long-term use. The oxidation mechanism of sulfur-containing compounds in the presence of polymeric heterogeneous catalysts of transition-metal oxides is confirmed. Microstructural characterization of the catalysts is performed by using X-ray computed tomography. The activity of various catalysts in the oxidation of sulfur-containing compounds is determined. We demonstrate the potential application of polymeric heterogeneous catalysts of transition-metal oxides in industrial wastewater treatment. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis and catalytic activity of Birnessite-Type Manganese Oxide synthesized by solvent-free method

    Science.gov (United States)

    Siregar, S. S.; Awaluddin, A.

    2018-04-01

    Redox reaction between KMnO4 and glucose usingsolvent-free method produces the octahedral layer birnessite-type manganese oxide. The effects of mole ratios, temperatures, and calcinations time on the structures and crystallinity of the oxides were studied throughthe X-ray powder diffraction analysis. The mole ratio of KMnO4/glucose (1:3) produces the purebirnessite with low crystallinity, whereas the mole ratio of KMnO4/glucose (3:1) yields high crystalline birnessite with minor components of hausmannite-type manganese oxide.The increasing of the temperature and calcinations times (300-700 °C and 3-7 h, respectively) willimprove the crystallinity and the purity of the as-synthesized oxide. Further experiments also showed that the as-syntesized octahedral layer birnessite-type manganese oxides have catalytic activity on the degradation of methylene blue (MB) dye with H2O2 as oxidant. The results revealed that the effective degradation could be achieved only in the presence of both the birnessite and H2O2, whereas without the addition of catalyst (H2O2only) or addition of H2O2 (catalyst only), the 3.5% and 15.5% of MB removal were obtained, respectively.

  11. Biogas Catalytic Reforming Studies on Nickel-Based Solid Oxide Fuel Cell Anodes

    DEFF Research Database (Denmark)

    Johnson, Gregory B.; Hjalmarsson, Per; Norrman, Kion

    2016-01-01

    of experiments were performed to study catalytic activity and effect of sulfur poisoning: (i) CH4 and CO2 dissociation; (ii) biogas (60% CH4 and 40% CO2) temperature-programmed reactions (TPRxn); and (iii) steady-state biogas reforming reactions followed by postmortem catalyst characterization by temperature......-programmed oxidation and time-of-flight secondary ion mass spectrometry. Results showed thatNi/ScYSZ/Pd-CGO was more active for catalytic dissociation of CH4 at 750°C and subsequent reactivity of deposited carbonaceous species. Sulfur deactivated most catalytic reactions except CO2 dissociation at 750°C. The presence...... of Pd-CGO helped to mitigate sulfur deactivation effect; e.g. lowering the onset temperature (up to 190°C) for CH4 conversion during temperature-programmed reactions. Both Ni/ScYSZ and Ni/ScYSZ/Pd-CGO anode catalysts were more active for dry reforming of biogas than they were for steam reforming...

  12. Partial Oxidation of Propylene over as Prepared and Acid Enriched Bi2Mo1-xWxO6 System

    Directory of Open Access Journals (Sweden)

    Shambhu Sakharam Parab

    2017-05-01

    Full Text Available The compounds Bi2Mo1-xWxO6 (x = 0.0, 0.2, and 0.4 were obtained through a Citrate sol-gel process. Thermogravimetric differential thermal analysis (TG-DTA, X-ray diffraction (XRD, Scanning electron microscopy (SEM and X-ray photoelectron spectroscopy (XPS techniques were used for characterization. Reitveld refinement of the XRD data confirmed the crystal structure of all the compositions to be orthorhombic, having Pca21 space group. XPS studies indicated the presence of +6 as well as +4 oxidation state for Mo. Surface acid enrichment of all the catalysts was done and monitored by NH3-TPD studies. Partial oxidation of propylene was studied over all the compounds. The W doping was found to increase the catalytic activity. Moreover, as-prepared catalysts and acid enriched catalysts were compared for their catalytic activity wherein, acid-enriched catalysts showed the improved conversion of propylene without hampering the product selectivity profile. Copyright © 2017 BCREC Group. All rights reserved Received: 16th September 2016; Revised: 1st December 2016; Accepted: 9th March 2017 How to Cite: Parab, S.S., Naik, S.J., Salker, A.V. (2017. Partial Oxidation of Propylene over as Prepared and Acid Enriched Bi2Mo1-xWxO6 System. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 197-205 (doi:10.9767/bcrec.12.2.702.197-205 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.702.197-205

  13. Mechanism for partial oxidation of Cyclohexene by Chromium (VI ...

    African Journals Online (AJOL)

    The oxidation of cyclohexene by chromium (VI) oxide in aqueous and acetic media has been studied. The reaction products were analysed using classical method, IR and GC/MS analyses. The major products of the oxidation reaction in acetic acid medium are cyclohexanol, cyclohexanone, cyclohex-2-en-1-one, ...

  14. Synthesis, characterization and catalytic evaluation of cubic ordered mesoporous iron-silicon oxides

    Energy Technology Data Exchange (ETDEWEB)

    Martins, T.S., E-mail: tsmartins@unifesp.br [Departamento de Ciencias Exatas e da Terra, Universidade Federal de Sao Paulo, Rua Prof. Artur Riedel 275, 09972-270 Diadema, Sao Paulo (Brazil); Mahmoud, A.; Cides da Silva, L.C. [Instituto de Quimica, Universidade de Sao Paulo, 05508-900 Sao Paulo (Brazil); Cosentino, I.C. [IPEN, Av. Prof. Lineu Prestes 2242, Cidade Universitaria, 05508-900 Sao Paulo (Brazil); Tabacniks, M.H. [Instituto de Fisica, Universidade de Sao Paulo 66318, 05315-970 Sao Paulo (Brazil); Matos, J.R. [Instituto de Quimica, Universidade de Sao Paulo, 05508-900 Sao Paulo (Brazil); Freire, R.S. [CEPEMA/USP, Centro de Capacitacao e Pesquisa em Meio Ambiente, Cubatao/SP (Brazil); Instituto de Quimica, Universidade de Sao Paulo, 05508-900 Sao Paulo (Brazil); Fantini, M.C.A. [Instituto de Fisica, Universidade de Sao Paulo 66318, 05315-970 Sao Paulo (Brazil)

    2010-11-01

    Iron was successfully incorporated in FDU-1 type cubic ordered mesoporous silica by a simple direct synthesis route. The (Fe/FDU-1) samples were characterized by Rutherford back-scattering spectrometry (RBS), small angle X-ray scattering (SAXS), N{sub 2} sorption isotherm, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The resulting material presented an iron content of about 5%. Prepared at the usual acid pH of -0.3, the composite was mostly formed by amorphous silica and hematite with a quantity of Fe{sup 2+} present in the structure. The samples prepared with adjusted pH values (2 and 3.5) were amorphous. The samples' average pore diameter was around 12.0 nm and BET specific surface area was of 680 m{sup 2} g{sup -1}. Although the iron-incorporated material presented larger lattice parameter, about 25 nm compared to pure FDU-1, the Fe/FDU-1 composite still maintained its cubic ordered fcc mesoporous structure before and after the template removal at 540 deg. C. The catalytic performance of Fe/FDU-1 was investigated in the catalytic oxidation of Black Remazol B dye using a catalytic ozonation process. The results indicated that Fe/FDU-1 prepared at the usual acid pH exhibited high catalytic activity in the mineralization of this pollutant when compared to the pure FDU-1, Fe{sub 2}O{sub 3} and Fe/FDU-1 prepared with higher pH of 2 and 3.5.

  15. Effects of Acid Treatment on the Acidic Properties and Catalytic Activity of MCM-41 for the Oxidative Dehydrogenation of Isobutane

    OpenAIRE

    Ehiro, Takuya; Itagaki, Ai; Misu, Hisanobu; Nakagawa, Keizo; Katoh, Masahiro; Katou, Yuuki; Ninomiya, Wataru; Sugiyama, Shigeru

    2016-01-01

    Mesoporous silicas have shown promise as materials for solid catalysts or catalyst supports due to their unique characteristics. Metal-doped mesoporous silicas are known to be catalytically active in the oxidative dehydrogenation (ODH) of isobutane. However, heavy-metal-free mesoporous silicas have not been studied closely for their use as catalysts. In the present study, MCM-41 (#41 Mobil composition of matter) was acid-treated to enhance its catalytic activity, although pure MCM-41 was conf...

  16. Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

    Science.gov (United States)

    Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T.

    2017-02-01

    In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (kapp), which is found to be 21.8, 26.2, and 8.7 (×10-3 s-1), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

  17. Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation.

    Science.gov (United States)

    Jodłowski, Przemysław J; Jędrzejczyk, Roman J; Chlebda, Damian K; Dziedzicka, Anna; Kuterasiński, Łukasz; Gancarczyk, Anna; Sitarz, Maciej

    2017-07-07

    The aim of this study was to obtain nanocrystalline mixed metal-oxide-ZrO₂ catalysts via a sonochemically-induced preparation method. The effect of a stabiliser's addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature.

  18. Promoting effect of vanadium on catalytic activity of Pt/Ce-Zr-O diesel oxidation catalysts.

    Science.gov (United States)

    Huang, Haifeng; Jiang, Bo; Gu, Lei; Qi, Zhonghua; Lu, Hanfeng

    2015-07-01

    A series of Pt-V/Ce-Zr-O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt-V/Ce-Zr-O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer-Emmett-Teller method, X-ray diffraction, H2 temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce-Zr-O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation. Copyright © 2015. Published by Elsevier B.V.

  19. Synthesis of ultrasmall Li-Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-10-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li-Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g-1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li-Mn spinel oxides obtained by conventional solid-state methods.

  20. Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-01-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li–Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g−1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li–Mn spinel oxides obtained by conventional solid-state methods. PMID:26456216

  1. Fabrication of highly catalytic silver nanoclusters/graphene oxide nanocomposite as nanotag for sensitive electrochemical immunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiamian; Wang, Xiuyun; Wu, Shuo, E-mail: wushuo@dlut.edu.cn; Song, Jie; Zhao, Yanqiu; Ge, Yanqiu; Meng, Changgong

    2016-02-04

    Silver nanoclusters and graphene oxide nanocomposite (AgNCs/GRO) is synthesized and functionalized with detection antibody for highly sensitive electrochemical sensing of carcinoembryonic antigen (CEA), a model tumor marker involved in many cancers. AgNCs with large surface area and abundant amount of low-coordinated sites are synthesized with DNA as template and exhibit high catalytic activity towards the electrochemical reduction of H{sub 2}O{sub 2}. GRO is employed to assemble with AgNCs because it has large specific surface area, super electronic conductivity and strong π-π stacking interaction with the hydrophobic bases of DNA, which can further improve the catalytic ability of the AgNCs. Using AgNCs/GRO as signal amplification tag, an enzyme-free electrochemical immunosensing protocol is designed for the highly sensitive detection of CEA on the capture antibody functionalized immunosensing interface. Under optimal conditions, the designed immunosensor exhibits a wide linear range from 0.1 pg mL{sup −1} to 100 ng mL{sup −1} and a low limit of detection of 0.037 pg mL{sup −1}. Practical sample analysis reveals the sensor has good accuracy and reproducibility, indicating the great application prospective of the AgNCs/GRO in fabricating highly sensitive immunosensors, which can be extended to the detection of various kinds of low abundance disease related proteins. - Highlights: • An enzyme-free electrochemical immunosensor is reported for detecting proteins. • A silver nanocluster/graphene oxide composite is synthesized as nanotag. • The nanotags exhibit highly catalytic activity to the electro-reduction of H{sub 2}O{sub 2}. • The as-fabricated immunosensor could detect protein in serum samples.

  2. A Novel Supramolecular Assembly Film of Porphyrin Bound DNA: Characterization and Catalytic Behaviors Towards Nitric Oxide

    Directory of Open Access Journals (Sweden)

    Osamu Ikeda

    2005-04-01

    Full Text Available A stable Fe(4-TMPyP-DNA-PADDA (FePyDP film was characterized onpyrolytic graphite electrode (PGE or an indium-tin oxide (ITO electrode through thesupramolecular interaction between water-soluble iron porphyrin (Fe(4-TMPyP and DNAtemplate, where PADDA (poly(acrylamide-co-diallyldimethylammonium chloride isemployed as a co-immobilizing polymer. Cyclic voltammetry of FePyDP film showed a pairof reversible FeIII/FeII redox peaks and an irreversible FeIV/FeIII peak at –0.13 V and 0.89vs. Ag|AgCl in pH 7.4 PBS, respectively. An excellent catalytic reduction of NO wasdisplayed at –0.61 V vs. Ag|AgCl at a FePyDP film modified electrode.Chronoamperometric experiments demonstrated a rapid response to the reduction of NOwith a linear range from 0.1 to 90 μM and a detection limit of 30 nM at a signal-to-noiseratio of 3. On the other hand, it is the first time to apply high-valent iron porphyrin ascatalyst at modified electrode for NO catalytic oxidation at 0.89 vs. Ag|AgCl. The sensorshows a high selectivity of some endogenous electroactive substances in biological systems.The mechanism of response of the sensors to NO is preliminary studied.

  3. Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity.

    Science.gov (United States)

    Arafa, Wael A A; Kärkäs, Markus D; Lee, Bao-Lin; Åkermark, Torbjörn; Liao, Rong-Zhen; Berends, Hans-Martin; Messinger, Johannes; Siegbahn, Per E M; Åkermark, Björn

    2014-06-28

    During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2(II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.

  4. Solid-oxide fuel cell operated on in situ catalytic decomposition products of liquid hydrazine

    Science.gov (United States)

    Gu, Hongxia; Ran, Ran; Zhou, Wei; Shao, Zongping; Jin, Wanqin; Xu, Nanping; Ahn, Jeongmin

    Hydrazine was examined as a fuel for a solid-oxide fuel cell (SOFC) that employed a typical nickel-based anode. An in situ catalytic decomposition of hydrazine at liquid state under room temperature and ambient pressure before introducing to the fuel cell was developed by applying a Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ (BSCF) oxide catalyst. Catalytic testing demonstrated that liquid N 2H 4 can be decomposed to gaseous NH 3 and H 2 at a favorable rate and at a temperature as low as 20 °C and H 2 selectivity reaching values as high as 10% at 60 °C. Comparable fuel cell performance was observed using either the in situ decomposition products of hydrazine or pure hydrogen as fuel. A peak power density of ∼850 mW cm -2 at 900 °C was obtained with a typical fuel cell composed of scandia-stabilized zirconia and La 0.8Sr 0.2MnO 3 cathode. The high energy and power density, easy storage and simplicity in fuel delivery make it highly attractive for portable applications.

  5. Theoretical study of catalytic mechanism for single-site water oxidation process.

    Science.gov (United States)

    Lin, Xiangsong; Hu, Xiangqian; Concepcion, Javier J; Chen, Zuofeng; Liu, Shubin; Meyer, Thomas J; Yang, Weitao

    2012-09-25

    Water oxidation is a linchpin in solar fuels formation, and catalysis by single-site ruthenium complexes has generated significant interest in this area. Combining several theoretical tools, we have studied the entire catalytic cycle of water oxidation for a single-site catalyst starting with [Ru(II)(tpy)(bpm)(OH(2))](2+) (i.e., [Ru(II)-OH(2)](2+); tpy is 2,2':6',2''-terpyridine and bpm is 2,2'-bypyrimidine) as a representative example of a new class of single-site catalysts. The redox potentials and pK(a) calculations for the first two proton-coupled electron transfers (PCETs) from [Ru(II)-OH(2)](2+) to [Ru(IV) = O](2+) and the following electron-transfer process to [Ru(V) = O](3+) suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [Ru(V) = O](3+) to generate [Ru(III)-OOH](2+), and H(3)O(+) with a low activation barrier (~10 kcal/mol). After the key O-O bond forming step in the single-site Ru catalysis, another PECT process oxidizes [Ru(III)-OOH](2+) to [Ru(IV)-OO](2+) when the pH is lower than 3.7. Two possible forms of [Ru(IV)-OO](2+), open and closed, can exist and interconvert with a low activation barrier (catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation.

  6. Characterizations of Platinum Catalysts Supported on Ce, Zr, Pr-oxides and Formation of Carbonate Species in Catalytic Wet Air Oxidation of Acetic Acid

    Czech Academy of Sciences Publication Activity Database

    Mikulová, Jana; Rossignol, S.; Barbier Jr., J.; Duprez, D.; Kappenstein, C.

    2007-01-01

    Roč. 124, 3-4 (2007), s. 185-190 ISSN 0920-5861 Institutional research plan: CEZ:AV0Z40720504 Keywords : acetic acid * cerium oxide * catalytic wet air oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.764, year: 2007

  7. Negative Effect of Calcination to Catalytic Performance of Coal Char-loaded TiO2 Catalyst in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2018-01-01

    How to Cite: Nurhadi, M., Kusumawardani, R., Nur, H. (2018. Negative Effect of Calcination to Catalytic Performance of Coal Char-loaded TiO2 Catalyst in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 113-118 (doi:10.9767/bcrec.13.1.1171.113-118

  8. Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater.

    Science.gov (United States)

    Melero, J A; Martínez, F; Botas, J A; Molina, R; Pariente, M I

    2009-09-01

    The aim of this work was to assess the treatment of wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using an Fe(2)O(3)/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80 degrees C using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for complete carbon depletion and initial pH of ca. 3 allow TOC degradation of around 50% after 200 min of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55h of reaction. Furthermore, the BOD(5)/COD ratio is increased from 0.20 to 0.30, whereas the average oxidation stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.

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

    International Nuclear Information System (INIS)

    Andrushkevich, T.V.

    1997-01-01

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

  10. Zeolite encapsulated Fe-porphyrin for catalytic oxidation with iodobenzene diacetate (PhI(OAc)2)

    International Nuclear Information System (INIS)

    Karimipour, G.; Rezaei, M.; Ashouri, D.

    2013-01-01

    meso-Tetrakis(3-pyridyl)porphyrin ato iron(III) chloride encapsulated on NaY Zeolite [Fe(T-3-PyP)-NaY] was synthesized as a heterogeneous ship-in-a-bottle type catalyst and characterized by Fourier transform infrared, atomic absorption, diffused reflectance UV-Vis, X-ray diffraction and scanning electron microscopy analysis. The catalytic activity of Fe(T-3-PyP-NaY was examined for the epoxidation of cyclohexene by PhI(OAc) 2 in CH 3 CN/H 2 O (5:1) and compared to that of Fe(T-3-PyP) as a homogeneous catalyst. We found that the heterogeneous catalyst Fe(T-3-PyP-NaY was stable and reusable for several times, and provided a mild condition and exhibited high activity and selectivity in the oxidation of alkenes to epoxides (16-94%). As representative examples for the use of Fe(T-3-PyP-NaY/ PhI(OAc) 2 in organic oxidations, oxidation of 4-nitro benzylalcohol to 4-nitrobenzaldehyde (97%), oxidative dehydrogenation of diethyl 4-(2,6-dichlorophenyl)-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate to the corresponding pyridine (100%), diphenylacetic acid to benzophenone (64%) was achieved. (Author)

  11. Catalytic oxidation of concentrated orange oil phase by synthetic metallic complexes biomimetic to MMO enzyme.

    Science.gov (United States)

    Fernandes, Ilizandra A; Esmelindro, Maria Carolina; Corazza, Marcos L; Franceschi, Elton; Treichel, Helen; de Oliveira, Debora; Frizzo, Caren D; Oliveira, J Vladimir

    2010-07-01

    This paper reports the catalytic oxidation of the concentrated orange oil phase using the complexes [Fe(III)(BMPP)Cl(micro-O)Fe(III)Cl(3)], [Cu(II)(BTMEA)(2)Cl]Cl and [Co(II)(BMPP)]Cl(2) biomimetic to methane monooxygenase enzyme as catalysts and hydrogen peroxide as oxidant. The reaction products of oil oxidation, mainly nootkatone, were identified by gas chromatography/mass spectrometry. A screening of catalysts was performed through a full 2(3) experimental design, varying the temperature from 30 to 70 degrees C, the catalyst concentration from 7.0 x 10(-4) to 1.5 x 10(-3) mol L(-1) and the oxidant/substrate molar ratio from 1:1 to 3:1. The results of reaction kinetics employing the most promising catalysts showed that conversions to nootkatone of up to 8% were achieved after 16 h at 70 degrees C. The results obtained in this study in terms of nootkatone production should be considered encouraging, since a real, industrially collected, raw material, instead of pure valencene, was employed in the reaction experiments, with a final content about ten times that present in the original concentrated oil.

  12. Fluorescent proteins such as eGFP lead to catalytic oxidative stress in cells

    Directory of Open Access Journals (Sweden)

    Douglas Ganini

    2017-08-01

    Full Text Available Fluorescent proteins are an important tool that has become omnipresent in life sciences research. They are frequently used for localization of proteins and monitoring of cells [1,2]. Green fluorescent protein (GFP was the first and has been the most used fluorescent protein. Enhanced GFP (eGFP was optimized from wild-type GFP for increased fluorescence yield and improved expression in mammalian systems [3]. Many GFP-like fluorescent proteins have been discovered, optimized or created, such as the red fluorescent protein TagRFP [4]. Fluorescent proteins are expressed colorless and immature and, for eGFP, the conversion to the fluorescent form, mature, is known to produce one equivalent of hydrogen peroxide (H2O2 per molecule of chromophore [5,6]. Even though it has been proposed that this process is non-catalytic and generates nontoxic levels of H2O2 [6], this study investigates the role of fluorescent proteins in generating free radicals and inducing oxidative stress in biological systems. Immature eGFP and TagRFP catalytically generate the free radical superoxide anion (O2•– and H2O2 in the presence of NADH. Generation of the free radical O2•– and H2O2 by eGFP in the presence of NADH affects the gene expression of cells. Many biological pathways are altered, such as a decrease in HIF1α stabilization and activity. The biological pathways altered by eGFP are known to be implicated in the pathophysiology of many diseases associated with oxidative stress; therefore, it is critical that such experiments using fluorescent proteins are validated with alternative methodologies and the results are carefully interpreted. Since cells inevitably experience oxidative stress when fluorescent proteins are expressed, the use of this tool for cell labeling and in vivo cell tracing also requires validation using alternative methodologies.

  13. Modeling the detailed kinetics of mitochondrial cytochrome c oxidase: Catalytic mechanism and nitric oxide inhibition.

    Science.gov (United States)

    Pannala, Venkat R; Camara, Amadou K S; Dash, Ranjan K

    2016-11-01

    Cytochrome c oxidase (CcO) catalyzes the exothermic reduction of O 2 to H 2 O by using electrons from cytochrome c, and hence plays a crucial role in ATP production. Although details on the enzyme structure and redox centers involved in O 2 reduction have been known, there still remains a considerable ambiguity on its mechanism of action, e.g., the number of sequential electrons donated to O 2 in each catalytic step, the sites of protonation and proton pumping, and nitric oxide (NO) inhibition mechanism. In this work, we developed a thermodynamically constrained mechanistic mathematical model for the catalytic action of CcO based on available kinetic data. The model considers a minimal number of redox centers on CcO and couples electron transfer and proton pumping driven by proton motive force (PMF), and accounts for the inhibitory effects of NO on the reaction kinetics. The model is able to fit well all the available kinetic data under diverse experimental conditions with a physiologically realistic unique parameter set. The model predictions show that: 1) the apparent K m of O 2 varies considerably and increases from fully reduced to fully oxidized cytochrome c depending on pH and the energy state of mitochondria, and 2) the intermediate enzyme states depend on pH and cytochrome c redox fraction and play a central role in coupling mitochondrial respiration to PMF. The developed CcO model can easily be integrated into existing mitochondrial bioenergetics models to understand the role of the enzyme in controlling oxidative phosphorylation in normal and disease conditions. Copyright © 2016 the American Physiological Society.

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  15. Partial oxidation of methane to methanol over catalyst ZSM-5 from coal fly ash and rice husk ash

    Directory of Open Access Journals (Sweden)

    Mirda Yanti Fusia

    2017-01-01

    Full Text Available Methane is one of the greenhouse gases that can be converted into liquid fuels such as methanol to retain most of the energy of methane and produce a cleaner environment. The conversion of methane to methanol using ZMS-5 represents a breakthrough in the utilization of methane. However, material sources for zeolite synthesis as catalyst usually are pro-analysis grade materials, which are expensive. Therefore, in this research, coal fly ash and rice husk ash were used as raw materials for mesoporous ZSM-5 zeolite synthesis. First, coal fly ash and rice husk were subjected to pre-treatment to extract silicate (SiO44− and aluminate (AlO45− and impurities separation. The ZSM-5 zeolite was synthesized through hydrothermal treatment using two types of templates. After ZSM-5 was synthesized, it was modified with Cobalt through impregnation method. The catalytic activity of both ZSM-5 and Co/ZSM-5 zeolites as heterogeneous catalysts in partial oxidation of methane were preliminary tested and compared with that commercial one. The result showed that the zeolite catalyst ZSM-5 from fly ash coal and rice husk ash has the potential to be used as catalysts in the partial oxidation of methane to methanol.

  16. Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

    Science.gov (United States)

    2015-07-21

    AFRL-OSR-VA-TR-2015-0195 CATALYSIS BY ATOMIC-SIZED CENTERS: METHANE ACTIVATION FOR PARTIAL OXIDATION AND COMBUSTION Horia Metiu UNIVERSITY OF...To) 01-04-2012 to 31-03-2015 4. TITLE AND SUBTITLE CATALYSIS BY ATOMIC-SIZED CENTERS: METHANE ACTIVATION FOR PARTIAL OXIDATION AND COMBUSTION 5a...livelink/llisapi.dll DISTRIBUTION A: Distribution approved for public release. Final Technical Report, FA9550-12-1-0147 “ CATALYSIS BY ATOMIC-SIZED

  17. Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation

    Science.gov (United States)

    Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Dok Kim, Young

    2018-04-01

    NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (˜20 m2 g-1) than expected for a flat-surface structure (present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

  18. Improved Aeration Process - Catalytic Role Of The Iron Oxides In Arsenic Oxidation And Coprecipitation

    DEFF Research Database (Denmark)

    Kowalski, Krysztof; Søgaard, Erik Gydesen

    2013-01-01

    Demands for a better drinking water quality, especially concerning arsenic, a compound with many adverse health effects, put a pressure on the utilities to ensure the best treatment technologies that meet nowadays and possible future quality standards. The aim of this paper is to introduce...... an improved aeration process that can also help in developing better arsenic removal treatment. The results present advantages of arsenic oxidation in an aeration process in the presence of ferrihydrite surface that have been shown to adsorb arsenic simultaneously to its oxidation. The presence...... of precipitated (ferrihydrite surface) and dissolved iron enhanced arsenic oxidation in comparison to solution with absence of precipitated iron in laboratory scale experiments. However, in the pilot scale studies the adsorption of arsenite on ferrihydrite was found to be the main process occurring during...

  19. Direct observation of enhanced plasmon-driven catalytic reaction activity of Au nanoparticles supported on reduced graphene oxides by SERS.

    Science.gov (United States)

    Liang, Xiu; You, Tingting; Liu, Dapeng; Lang, Xiufeng; Tan, Enzhong; Shi, Jihua; Yin, Penggang; Guo, Lin

    2015-04-21

    Graphene-based nanocomposites have recently attracted tremendous research interest in the field of catalysis due to their unique optical and electronic properties. However, direct observation of enhanced plasmon-driven catalytic activity of Au nanoparticles (NPs) supported on reduced graphene oxides (Au/rGO) has rarely been reported. Herein, based on the reduction from 4-nitrobenzenethiol (4-NBT) to p,p'-dimercaptoazobenzene (DMAB), the catalytic property of Au/rGO nanocomposites was investigated and compared with corresponding Au NP samples with similar size distribution. Our results show that Au/rGO nanocomposites could serve as a good catalytic and analytic platform for plasmon-driven chemical reactions. In addition, systematic comparisons were conducted during power- and time-dependent surface-enhanced Raman scattering (SERS) experiments, which exhibited a lower power threshold and higher catalytic efficiency for Au/rGO as compared to Au NPs toward the reaction.

  20. Insights into catalytic oxidation at the Au/TiO(2) dual perimeter sites.

    Science.gov (United States)

    Green, Isabel X; Tang, Wenjie; Neurock, Matthew; Yates, John T

    2014-03-18

    Gold (Au) nanoparticles supported on reducible oxides such as TiO2 demonstrate exceptional catalytic activity for a wide range of gas phase oxidation reactions such as CO oxidation, olefin epoxidation, and water gas shift catalysis. Scientists have recently shifted their hypotheses on the origin of the reactivity of these materials from the unique electronic properties and under-coordinated Au sites on nanometer-sized particles to bifunctional sites at the Au-support interface. In this Account, we summarize our recent experimental and theoretical results to provide insights into the active sites and pathways that control oxidation over Au/TiO2 catalysts. We provide transmission IR spectroscopic data that show the direct involvement of the Au-Ti(4+) dual perimeter sites, and density functional theory results that connect the electronic properties at these sites to their reactivity and to plausible reaction mechanisms. We also show the importance of interfacial Au-Ti(4+) sites in adsorbing and activating O2 as a result of charge transfer from the Au into antibonding states on O2 causing di-σ interactions with interfacial Au-Ti(4+) sites. This results in apparent activation energies for O2 activation of 0.16-0.60 eV thus allowing these materials to operate over a wide range of temperatures (110-420 K) and offering the ability also to control H-H, C-H, and C-O bond scission. At low temperatures (100-130 K), adsorbed O2 directly reacts with co-adsorbed CO or H2. In addition, we observe the specific consumption of CO adsorbed on TiO2. The more strongly held CO/Au species do not react at ∼120 K due to high diffusion barriers that prevent them from reaching active interfacial sites. At higher temperatures, O2 directly dissociates to form active oxygen adatoms (O*) on Au and TiO2. These readily react with bound hydrocarbon intermediates via base-catalyzed nucleophilic attack on unsaturated C═O and C═C bonds or via activation of weakly acidic C-H or O-H bonds. We

  1. Identification of Subnanometric Ag Species, Their Interaction with Supports and Role in Catalytic CO Oxidation

    Directory of Open Access Journals (Sweden)

    Yulia Kotolevich

    2016-04-01

    Full Text Available The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals.

  2. Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhan, Wangcheng [East China Univ. of Science and Technology, Shanghai (China); Wang, Jinglin [East China Univ. of Science and Technology, Shanghai (China); Wang, Haifeng [East China Univ. of Science and Technology, Shanghai (China); Zhang, Jinshui [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Liu, Xiaofei [East China Univ. of Science and Technology, Shanghai (China); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zhang, Pengfei [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chi, Miaofang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Guo, Yanglong [East China Univ. of Science and Technology, Shanghai (China); Guo, Yun [East China Univ. of Science and Technology, Shanghai (China); Lu, Guanzhong [East China Univ. of Science and Technology, Shanghai (China); Sun, Shouheng [Brown Univ., Providence, RI (United States); Dai, Sheng [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Zhu, Huiyuan [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-06-07

    Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air, the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.

  3. Characterization of microstructure and catalytic of cerium oxide obtained by colloidal solution

    International Nuclear Information System (INIS)

    Senisse, C.A.L.; Bergmann, C.P.; Alves, A.K.

    2012-01-01

    This study investigated to obtain particles of cerium oxide, for use as catalysts for the combustion of methane using the technique of through polymeric colloidal solution. Obtaining the colloidal system is based on hydrolysis of salts such as cerium acetylacetonate, cerium nitrate in the presence of additives such as polyvinylbutyral (PVB), polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVA), at concentrations of 5, 10 and 15% in aqueous or alcoholic medium. These solutions containing ions of interest were subjected to a heat treatment at 650° C for 30 minutes, with heating rate of 2 ° C/ min. After heat treatment, the fibers were characterized according to their morphology, surface area, crystallinity, weight loss and catalytic activity. Samples obtained from cerium acetylacetonate were more reactive than the cerium nitrate to the combustion of methane, as showed greater conversions and higher temperatures reached during the process, which is of utmost importance since the combustion catalytic methane is used for generating thermal energy. After the reaction with methane, the samples underwent significant change in surface area, probably due to the intensity of combustion reactions of the nitrate and the generation of heat involved in this reaction, which gave rise to coarse particles. During the combustion process using the obtained from particles of cerium acetylacetonate, there was the release of large quantities of nitrogen compared to the results of assays with the particles obtained with cerium nitrate. (author)

  4. Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

    International Nuclear Information System (INIS)

    Zhan, Wangcheng; Wang, Jinglin; Wang, Haifeng; Zhang, Jinshui; Liu, Xiaofei

    2017-01-01

    Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air, the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.

  5. Modeling of adsorber/desorber/catalytic reactor system for ethylene oxide removal

    Directory of Open Access Journals (Sweden)

    ZELJKO B. GRBAVCIC

    2004-12-01

    Full Text Available The removal of ethylene oxide (EtO in a combined system adsorber/desorber/catalytic reactor has been investigated. The combined system was a modified draft tube spouted bed reactor loaded with Pt/Al2O3 catalyst. The annular region was divided into two sectons, the “hot” section contained about 7 % of catalyst and it behaved as a desorber and catalytic incinerator, while the “cold” section, with the rest of the catalyst, behaved as a sorber. The catalyst particles were circulated between the two sections by use of a draft tube riser. The Computational Fluid Dynamics (CFD program package FLUENT was used for simulations of the operation of the combined system. In addition, a one-dimensional numerical model for the operation of the packed bed reactor was compared with the corresponding FLUENT calculations. The results of the FLUENT simulations are in very good agreement with the experimental observations, as well as with the results of the one-dimensional numerical simulations.

  6. Kinetic spectrophotometric determination of iron based on catalytic oxidation of p-acetylarsenazo

    Directory of Open Access Journals (Sweden)

    Qing-Zhou Zhai

    2009-12-01

    Full Text Available A novel catalytic kinetic spectrophotometric method for the determination of iron is developed based on the catalytic effect of Fe(III on the oxidation reaction of p-acetylarsenazo(ASApA by potassium periodate. Maximum absorbance of the Fe(III−ASApA−KIO4 system in 8.0 × 10-3 M sulfuric acid occurs at the wavelength of 540 nm. The change in absorbance (ΔA is linearly related with the concentration of iron(III in the range of 0.10−4.0 ng/mL and fitted the equation: ΔA = 4.91 × 10-2 C (C: ng/mL + 0.017, with a regression coefficient of 0.9966 at the wavelength. The detection limit of the method is 0.031 ng/mL. The relative standard deviation of the method was from 1.34% to 1.78% for 11 replicate determinations. The standard addition recovery of the method ranged from 95.71% to 103.3%. The method was used to determine iron in the black gingili paste, oat slice, sleeve-fish silk food samples. The determined results were in agreement with those by atomic absorption spectrometry.

  7. Fabrication of highly catalytic silver nanoclusters/graphene oxide nanocomposite as nanotag for sensitive electrochemical immunoassay.

    Science.gov (United States)

    Wang, Jiamian; Wang, Xiuyun; Wu, Shuo; Song, Jie; Zhao, Yanqiu; Ge, Yanqiu; Meng, Changgong

    2016-02-04

    Silver nanoclusters and graphene oxide nanocomposite (AgNCs/GRO) is synthesized and functionalized with detection antibody for highly sensitive electrochemical sensing of carcinoembryonic antigen (CEA), a model tumor marker involved in many cancers. AgNCs with large surface area and abundant amount of low-coordinated sites are synthesized with DNA as template and exhibit high catalytic activity towards the electrochemical reduction of H2O2. GRO is employed to assemble with AgNCs because it has large specific surface area, super electronic conductivity and strong π-π stacking interaction with the hydrophobic bases of DNA, which can further improve the catalytic ability of the AgNCs. Using AgNCs/GRO as signal amplification tag, an enzyme-free electrochemical immunosensing protocol is designed for the highly sensitive detection of CEA on the capture antibody functionalized immunosensing interface. Under optimal conditions, the designed immunosensor exhibits a wide linear range from 0.1 pg mL(-1) to 100 ng mL(-1) and a low limit of detection of 0.037 pg mL(-1). Practical sample analysis reveals the sensor has good accuracy and reproducibility, indicating the great application prospective of the AgNCs/GRO in fabricating highly sensitive immunosensors, which can be extended to the detection of various kinds of low abundance disease related proteins. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Catalytic and recyclability properties of phytogenic copper oxide nanoparticles derived from Aglaia elaeagnoidea flower extract

    Directory of Open Access Journals (Sweden)

    G. Manjari

    2017-07-01

    Full Text Available The phytogenic synthesis method to highly active, recoverable and recyclable heterogeneous copper oxide nanocatalyst and encapsulated within biomaterial that acts as a nontoxic and renewable source of reducing and stabilizing agent. The biosynthesized CuO NPs were characterized using UV–Vis absorption spectroscopy, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, energy dispersive X-ray spectroscopy (EDX, transmission electron microscopy (TEM and thermo gravimetric analysis-differential scanning calorimetry (TGA–DSC, techniques. The formation of CuO NPs with the size 20–45 nm range is shown in TEM image. Significantly, in aqueous phase CuO NPs have high catalytic activity for the reduction of Congo red (CR, methylene blue (MB and 4-nitrophenol (4-NP in the presence of the sodium borohydride (NaBH4 at room temperature. In addition, CuO NPs catalyst can be easily recovered by centrifugation and reused for 6 cycles with more than 90% conversion efficiency. CuO nanocatalyst, leaching after catalytic application was investigated by ICPAES (Inductively coupled plasma atomic emission spectroscopy. CuO NPs possess great prospects in reduction of pernicious dyes and nitro organic pollutants in water.

  9. Reaction Mechanism for the Formation of Nitrogen Oxides (NO x ) During Coke Oxidation in Fluidized Catalytic Cracking Units

    KAUST Repository

    Chaparala, Sree Vidya

    2015-06-11

    Fluidized catalytic cracking (FCC) units in refineries process heavy feedstock obtained from crude oil distillation. While cracking feed, catalysts get deactivated due to coke deposition. During catalyst regeneration by burning coke in air, nitrogen oxides (NOx) are formed. The increase in nitrogen content in feed over time has resulted in increased NOx emissions. To predict NOx concentration in flue gas, a reliable model for FCC regenerators is needed that requires comprehensive understanding and accurate kinetics for NOx formation. Based on the nitrogen-containing functional groups on coke, model molecules are selected to study reactions between coke-bound nitrogen and O2 to form NO and NO2 using density functional theory. The reaction kinetics for the proposed pathways are evaluated using transition state theory. It is observed that the addition of O2 on coke is favored only when the free radical is present on the carbon atom instead of nitrogen atom. Thus, NOx formation during coke oxidation does not result from the direct attack by O2 on N atoms of coke, but from the transfer of an O atom to N from a neighboring site. The low activation energies required for NO formation indicate that it is more likely to form than NO2 during coke oxidation. The favorable pathways for NOx formation that can be used in FCC models are identified. Copyright © 2015 Taylor & Francis Group, LLC.

  10. Synthesis, Characterization and Shape-Dependent Catalytic CO Oxidation Performance of Ruthenium Oxide Nanomaterials: Influence of Polymer Surfactant

    Directory of Open Access Journals (Sweden)

    Antony Ananth

    2015-08-01

    Full Text Available Ruthenium oxide nano-catalysts supported on mesoporous γ-Al2O3 have been prepared by co-precipitation method and tested for CO oxidation. The effect of polyethylene glycol (PEG on the properties of the catalyst was studied. Addition of the PEG surfactant acted as a stabilizer and induced a change in the morphology of ruthenium oxide from spherical nanoparticles to one-dimensional nanorods. Total CO conversion was measured as a function of morphology at 175 °C and 200 °C with 1.0 wt.% loading for PEG-stabilized and un-stabilized catalysts, respectively. Conversion routinely increased with temperature but in each case, the PEG-stabilized catalyst exhibited a notably higher catalytic activity as compared to the un-stabilized equivalent. It can be assumed that the increase in the activity is due to the changes in porosity, shape and dispersion of the catalyst engendered by the use of PEG.

  11. Peroxynitrite formation in nitric oxide-exposed submitochondrial particles: detection, oxidative damage and catalytic removal by Mn-porphyrins.

    Science.gov (United States)

    Valez, Valeria; Cassina, Adriana; Batinic-Haberle, Ines; Kalyanaraman, Balaraman; Ferrer-Sueta, Gerardo; Radi, Rafael

    2013-01-01

    Peroxynitrite (ONOO(-)) formation in mitochondria may be favored due to the constant supply of superoxide radical (O(2)(∙-)) by the electron transport chain plus the facile diffusion of nitric oxide ((∙)NO) to this organelle. Herein, a model system of submitochondrial particles (SMP) in the presence of succinate plus the respiratory inhibitor antimycin A (to increase O(2)(∙-) rates) and the (∙)NO-donor NOC-7 was studied to directly establish and quantitate peroxynitrite by a multiplicity of methods including chemiluminescence, fluorescence and immunochemical analysis. While all the tested probes revealed peroxynitrite at near stoichiometric levels with respect to its precursor radicals, coumarin boronic acid (a probe that directly reacts with peroxynitrite) had the more straightforward oxidation profile from O(2)(∙-)-forming SMP as a function of the (∙)NO flux. Interestingly, immunospintrapping studies verified protein radical generation in SMP by peroxynitrite. Substrate-supplemented SMP also reduced Mn(III)porphyrins (MnP) to Mn(II)P under physiologically-relevant oxygen levels (3-30 μM); then, Mn(II)P were capable to reduce peroxynitrite and protect SMP from the inhibition of complex I-dependent oxygen consumption and protein radical formation and nitration of membranes. The data directly support the formation of peroxynitrite in mitochondria and demonstrate that MnP can undergo a catalytic redox cycle to neutralize peroxynitrite-dependent mitochondrial oxidative damage. Copyright © 2012 Elsevier Inc. All rights reserved.

  12. Platinum Catalysts Supported on Ce, Zr, Pr - Oxides in Catalytic Wet Air Oxidation of Acetic Acid

    Czech Academy of Sciences Publication Activity Database

    Mikulová, Jana; Rossignol, S.; Barbier Jr., J.; Duprez, D.; Kappenstein, C.

    2007-01-01

    Roč. 146, č. 3 (2007), s. 1248-1253 ISSN 0304-3894 Institutional research plan: CEZ:AV0Z40720504 Keywords : platinum * cerium oxide * carbonate species Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.337, year: 2007

  13. Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

    Energy Technology Data Exchange (ETDEWEB)

    Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T., E-mail: dhnaraj_masram27@rediffmail.com

    2017-02-28

    Highlights: • AuNPs on PDMAEMA brushes immobilized reduced graphene oxide was used as catalyst. • A novel highly efficient, reusable heterogeneous catalyst for dyes degradation. • Rhodamine B, Methyl Orange and Eosin Y was used for study. • Apparent rate constant observed was 21.8, 26.2, and 8.7 (×10{sup −3} s{sup −1}) respectively. - Abstract: In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (k{sub app}), which is found to be 21.8, 26.2, and 8.7 (×10{sup −3} s{sup −1}), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

  14. Removal of radionuclides from partitioning waste solutions by adsorption and catalytic oxidation methods

    Energy Technology Data Exchange (ETDEWEB)

    Yamagishi, Isao; Yamaguchi, Isoo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kubota, Masumitsu [Research Organization for Information Science and Technology (RIST), Tokai, Ibaraki (Japan)

    2000-09-01

    Adsorption of radionuclides with inorganic ion exchangers and catalytic oxidation of a complexant were studied for the decontamination of waste solutions generated in past partitioning tests with high-level liquid waste. Granulated ferrocyanide and titanic acid were used for adsorption of Cs and Sr, respectively, from an alkaline solution resulting from direct neutralization of an acidic waste solution. Both Na and Ba inhibited adsorption of Sr but Na did not that of Cs. These exchangers adsorbed Cs and Sr at low concentration with distribution coefficients of more than 10{sup 4}ml/g from 2M Na solution of pH11. Overall decontamination factors (DFs) of Cs and total {beta} nuclides exceeded 10{sup 5} and 10{sup 3}, respectively, at the neutralization-adsorption step of actual waste solutions free from a complexant. The DF of total {alpha} nuclides was less than 10{sup 3} for a waste solution containing diethylenetriaminepentaacetic acid (DTPA). DTPA was rapidly oxidized by nitric acid in the presence of a platinum catalyst, and radionuclides were removed as precipitates by neutralization of the resultant solution. The DF of {alpha} nuclides increased to 8x10{sup 4} by addition of the oxidation step. The DFs of Sb and Co were quite low through the adsorption step. A synthesized Ti-base exchanger (PTC) could remove Sb with the DF of more than 4x10{sup 3}. (author)

  15. Catalytic oxidation of xanthine by the nanostructured poly(aniline-co-2,4-diaminophenol)

    Energy Technology Data Exchange (ETDEWEB)

    Yang Yifei [Department of Chemistry, Yangzhou University, Yangzhou 225002 (China); Mu Shaolin, E-mail: slmu@yzu.edu.c [Department of Chemistry, Yangzhou University, Yangzhou 225002 (China)

    2010-06-30

    Poly(aniline-co-2,4-diaminophenol) (PADAP) was synthesized in a solution containing aniline, 2,4-diaminophenol (DAP) and sulfuric acid, using potentiostatic method. The image of a PADAP film is constructed of spherical particles with an average diameter of 50 nm, which was examined by both scanning electron microscope (SEM) and atomic force microscopy (AFM). The nanostructured PADAP can catalyze xanthine oxidation under a less positive potential of 0.31 V (vs. SCE), which was proved by cyclic voltammetry and amperometric method. The PADAP electrode has a very fast response for the determination of xanthine. The response current of the PADAP electrode increases with increasing xanthine concentration and applied potential. The catalytic mechanism for the oxidation of xanthine on the nanostructured PADAP electrode is similar to that of xanthine oxidase-catalyzed reaction. Experimental evidence for the electrocatalytic mechanism of xanthine oxidation on a PADAP electrode was demonstrated via measurements of the open-circuit potential and the in situ chemical-ESR spectra of PADAP in the solutions without and with xanthine, respectively.

  16. Dynamic\tmodelling of catalytic three-phase reactors for hydrogenation and oxidation processes

    Directory of Open Access Journals (Sweden)

    Salmi T.

    2000-01-01

    Full Text Available The dynamic modelling principles for typical catalytic three-phase reactors, batch autoclaves and fixed (trickle beds were described. The models consist of balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. Rate equations, transport models and mass balances were coupled to generalized heterogeneous models which were solved with respect to time and space with algorithms suitable for stiff differential equations. The aspects of numerical solution strategies were discussed and the procedure was illustrated with three case studies: hydrogenation of aromatics, hydrogenation of aldehydes and oxidation of ferrosulphate. The case studies revealed the importance of mass transfer resistance inside the catalyst pallets as well as the dynamics of the different phases being present in the reactor. Reliable three-phase reactor simulation and scale-up should be based on dynamic heterogeneous models.

  17. Catalytic oxidation efficiencies for tritium and tritiated methane in a mature, industrial-scale decontamination system

    International Nuclear Information System (INIS)

    Mintz, J.M.; Gildea, P.D.

    1981-01-01

    Almost all tritium decontamination systems proposed for fusion facilities employ catalytic oxidation to water, followed by drying, to remove tritium and tritiated hydrocarbons from gas streams. One such large-scale system, the gas purification system (GPS), has been operating in the Tritium Research Laboratory (TRL) at Sandia National Laboratories, Livermore, CA, since October 1977. A series of experiments have recently been conducted there to assesss the current operating characteristics of the GPS catalyst. The experiments used tritium and tritiated methane and covered a range of temperatures, flow rates, and concentration levels. When contrasted with 1977 data, the results indicate that no measurable degradation of catalyst function had occurred. However, some reduction in active metal surface area, as indicated by B.E.T. surface area measurements (approx. 100 → 90m 2 /g) and AES scans (approx. 1.4 → 0.9 at. % Pt), had occurred. Kinetic rate coefficients were also derived and a rough temperature dependence obtained

  18. Catalytic oxidation efficiencies for tritium and tritiated methane in a mature, industrial-scale decontamination system

    International Nuclear Information System (INIS)

    Mintz, J.M.; Gildea, P.D.

    1980-10-01

    Almost all tritium decontamination systems proposed for fusion facilities employ catalytic oxidation to water, followed by drying, to remove tritium and tritiated hydrocarbons from gas streams. One such large-scale system, the gas purification system (GPS), has been operating in the Tritium Research Laboratory (TRL) at Sandia National Laboratories, Livermore, CA, since October 1977. A series of experiments have recently been conducted there to assess the current operating characteristics of the GPS catalyst. The experiments used tritium and tritiated methane and covered a range of temperatures, flow rates, and concentration levels. When contrasted with 1977 data, the results indicate that no measurable degradation of catalyst function had occurred. However, some reduction in active metal surface area, as indicated by B.E.T. surface area measurements (approx. 100 → 90 m 2 /g) and AES scans (approx. 1.4 → 0.9 at% Pt), had occurred. Kinetic rate coefficients were also derived and a rough temperature dependence obtained

  19. Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting.

    Science.gov (United States)

    Rausch, Benjamin; Symes, Mark D; Chisholm, Greig; Cronin, Leroy

    2014-09-12

    The electrolysis of water using renewable energy inputs is being actively pursued as a route to sustainable hydrogen production. Here we introduce a recyclable redox mediator (silicotungstic acid) that enables the coupling of low-pressure production of oxygen via water oxidation to a separate, catalytic hydrogen production step outside the electrolyzer that requires no post-electrolysis energy input. This approach sidesteps the production of high-pressure gases inside the electrolytic cell (a major cause of membrane degradation) and essentially eliminates the hazardous issue of product gas crossover at the low current densities that characterize renewables-driven water-splitting devices. We demonstrated that a platinum-catalyzed system can produce pure hydrogen over 30 times faster than state-of-the-art proton exchange membrane electrolyzers at equivalent platinum loading. Copyright © 2014, American Association for the Advancement of Science.

  20. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  1. Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

    Directory of Open Access Journals (Sweden)

    Kabljanac, Ž.

    2011-11-01

    Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

  2. Effects of Mn- and K-addition on catalytic activity of calcium oxide for methane activation

    International Nuclear Information System (INIS)

    Park, Jong Sik; Kong, Jang Il; Lee, Sung Han; Jun, Jong Ho

    1998-01-01

    Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800 .deg. C to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction (XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally p(CH 4 )/p(O 2 )=250 Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best C 2 yield of 8.0% with a selectivity of 43.2% at 775 .deg. C. The C 2 selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO((Mn)>6.3 mol%)catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the C 2 selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000 .deg. C at Po2's of 10 -3 to 10 -1 atm. The electrical conductivity was decreased with Mn-doping and increased with increasing Po 2 in the range of 10 -3 to 10 -1 atm, indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry

  3. Atomistic structure of cobalt-phosphate nanoparticles for catalytic water oxidation.

    Science.gov (United States)

    Hu, Xiao Liang; Piccinin, Simone; Laio, Alessandro; Fabris, Stefano

    2012-12-21

    Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co-O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO(6) octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ~1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs-which are believed to be essential for the catalytic activity-display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

  4. Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

    Science.gov (United States)

    Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

    2018-03-01

    Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

  5. Oxidative destruction of biomolecules by gasoline engine exhaust products and detoxifying effects of the three-way catalytic converter.

    Science.gov (United States)

    Blaurock, B; Hippeli, S; Metz, N; Elstner, E F

    1992-01-01

    Aqueous solutions of engine exhaust condensation products were derived from cars powered by diesel or four-stroke gasoline engines (with and without three-way catalytic converter). The cars were operated on a static test platform. Samples of the different exhaust solutions accumulated in a Grimmer-type distillation trap (VDI 3872) during standard test programs (Federal Test Procedure) were incubated with important biomolecules. As indicators of reactive oxygen species or oxidative destruction, ascorbic acid, cysteine, glutathione, serum albumin, the enzymes glycerinaldehyde phosphate dehydrogenase and xanthine oxidase, and the oxygen free-radical indicator keto-methylthiobutyrate were used. During and after the incubations, oxygen activation (consumption) and oxidative destruction were determined. Comparison of the oxidative activities of the different types of exhaust condensates clearly showed that the exhaust condensate derived from the four-stroke car equipped with a three-way catalytic converter exhibited by far the lowest oxidative and destructive power.

  6. Consideration of the Role of Plasma in a Plasma-Coupled Selective Catalytic Reduction of Nitrogen Oxides with a Hydrocarbon Reducing Agent

    Directory of Open Access Journals (Sweden)

    Byeong Ju Lee

    2017-10-01

    Full Text Available The purpose of this study is to explain how plasma improves the performance of selective catalytic reduction (SCR of nitrogen oxides (NOx with a hydrocarbon reducing agent. In the plasma-coupled SCR process, NOx reduction was performed with n-heptane as a reducing agent over Ag/γ-Al2O3 as a catalyst. We found that the plasma decomposes n-heptane into several oxygen-containing products such as acetaldehyde, propionaldehyde and butyraldehyde, which are more reactive than the parent molecule n-heptane in the SCR process. Separate sets of experiments using acetaldehyde, propionaldehyde and butyraldehyde, one by one, as a reductant in the absence of plasma, have clearly shown that the presence of these partially oxidized compounds greatly enhanced the NOx conversion. The higher the discharge voltage, the more the amounts of such partially oxidized products. The oxidative species produced by the plasma easily converted NO into NO2, but the increase of the NO2 fraction was found to decrease the NOx conversion. Consequently, it can be concluded that the main role of plasma in the SCR process is to produce partially oxidized compounds (aldehydes, having better reducing power. The catalyst-alone NOx removal efficiency with n-heptane at 250 °C was measured to be less than 8%, but it increased to 99% in the presence of acetaldehyde at the same temperature. The NOx removal efficiency with the aldehyde reducing agent was higher as the number of carbons in the aldehyde was more; for example, the NOx removal efficiencies at 200 °C with butyraldehyde, propionaldehyde and acetaldehyde were measured to be 83.5%, 58.0% and 61.5%, respectively, which were far above the value (3% obtained with n-heptane.

  7. The catalytic oxidation of H2S in a stainless steel membrane reactor with separate feed of reactants.

    NARCIS (Netherlands)

    Neomagus, H.W.J.P.; van Swaaij, Willibrordus Petrus Maria; Versteeg, Geert

    1998-01-01

    The oxidation of H2S is studied in a membrane reactor with separate feed of reactants. As a novelty in the concept of separate introduction of the reactants, a sintered stainless steel membrane is used, because this type of material is easy to integrate into the reactor, and the catalytic properties

  8. The catalytic oxidation of H2S in a stainless steel membrane reactor with separate feed of reactants

    NARCIS (Netherlands)

    Neomagus, H.W.J.P.; Swaaij, W.P.M. van; Versteeg, G.F.

    1998-01-01

    The oxidation of H2S is studied in a membrane reactor with separate feed of reactants. As a novelty in the concept of separate introduction of the reactants, a sintered stainless steel membrane is used, because this type of material is easy to integrate into the reactor, and the catalytic properties

  9. Oxidation of Borneol to Camphor Using Oxone and Catalytic Sodium Chloride: A Green Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Lang, Patrick T.; Harned, Andrew M.; Wissinger, Jane E.

    2011-01-01

    A new green oxidation procedure was developed for the undergraduate organic teaching laboratories using Oxone and a catalytic quantity of sodium chloride for the conversion of borneol to camphor. This simple 1 h, room temperature reaction afforded high quality and yield of product, was environmentally friendly, and produced negligible quantities…

  10. Construction and biofunctional evaluation of electrospun vascular graft loaded with selenocystamine for in situ catalytic generation of nitric oxide

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Siyuan; An, Jun; Weng, Lei [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China); Li, Yandong [Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin 300071 (China); Xu, Han; Wang, Yaping; Ding, Dan; Kong, Deling [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China); Wang, Shufang, E-mail: wangshufang@nankai.edu.cn [State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Bioactive Materials for Ministry of Education, College of Life Sciences, Nankai University, Tianjin 300071 (China)

    2014-12-01

    Construction and biofunctional evaluation of a novel vascular graft with in situ catalytic generation of nitric oxide were described in this paper. Poly α-lysine and poly (γ-glutamic acid) were deposited alternately onto the surface of an electrospun poly ε-caprolactone matrix via electrostatic layer-by-layer self-assembly, and then selenocystamine was loaded as a catalyst. Measurement of in vitro catalytic generation of nitric oxide demonstrated that this catalyst-loaded material could considerably accelerate the release of nitric oxide from S-nitrosoglutathione. A fibroblast proliferation assay showed that the material possessed satisfactory cellular compatibility. The catalyst-loaded material could inhibit the spread of smooth muscle cells in the presence of nitric oxide donors. In arteriovenous-shunt experiment, the catalyst-loaded graft exhibited good anti-thrombotic property where it could prevent acute thrombosis by decreasing the adhesion and activation of platelets and other blood cells. These data suggest a new method of building vascular grafts with improved hemocompatibility and biological functions. - Highlights: • A porous small-diameter vascular graft was prepared by electrospinning. • Selenocystamine was loaded for in situ catalytic and sustained NO generation. • There was a significant catalytic NO generation on the catalyst-loaded sample. • The spread of smooth muscle cells was inhibited on the catalyst-loaded sample. • The catalyst-loaded sample showed anti-thrombotic property in AV-shunt experiment.

  11. Treatment of organic pollutants in coke plant wastewater by the method of ultrasonic irradiation, catalytic oxidation and activated sludge

    NARCIS (Netherlands)

    Ning, Ping; Bart, Hans-Jörg; Jiang, Yijiao; de Haan, A.B.; Tien, C.

    2005-01-01

    The paper deals with the degradation of the organic pollutants in coke plant wastewater by the combination process of ultrasonic irradiation, catalytic oxidation and activated sludge. The effect factors of ultrasonic irradiation on the degradation of the organic pollutants such as saturating gas,

  12. Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

    In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable

  13. Direct Partial Oxidation of Natural Gas to Liquid Chemicals

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund

    2007-01-01

    Direkte delvis oxidation af naturgas til flydende kemikalier er en attraktiv industriel proces, hvor naturgas omdannes til stoffer; primært methanol (CH3OH) som let kan transporteres over store afstande. Omdannelsen sker i en simpel et-trinsproces under højt tryk, lave forbrændingstemperaturer, s...

  14. mechanism for partial oxidation of cyclohexene by chromium (vi)

    African Journals Online (AJOL)

    DJFLEX

    detection limit of the classical test but was detected by the IR spectroscopic test. The unsaturation detected by decolourisation of the permanganate may be from the allylic ketone. GC/MS Analysis of Cyclohexene Oxidation Products. The chromatogram gave eleven (11) distinct peaks. On comparing the MS spectrum of each ...

  15. Valorization of Lignin by Partial Wet Oxidation Using Sustainable Heteropoly Acid Catalysts

    Directory of Open Access Journals (Sweden)

    Abayneh Getachew Demesa

    2017-09-01

    Full Text Available The production of carboxylic acids by partial wet oxidation of alkali lignin at elevated temperatures and pressures was studied experimentally. Two different heteropoly acids, phosphotungstic acid (H3PW12O40 and phosphomolybdic acid (H3PMo12O40, were used to catalyze the oxidation of lignin under hydrothermal conditions. Factors influencing the total yield of carboxylic acids formed during the partial oxidation of lignin were investigated. Formic, acetic and succinic acids were the major products identified. Of the two catalysts used, phosphomolybdic acid gave the most promising results, with carboxylic acid yields and lignin conversions of up to 45% and 95%, respectively.

  16. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant

    Directory of Open Access Journals (Sweden)

    Mukhamad Nurhadi

    2017-04-01

    Full Text Available The modified coal char from low-rank coal by sulfonation, titanium impregnation and followed by alkyl silylation possesses high catalytic activity in styrene oxidation. The surface of coal char was undergone several steps as such: modification using concentrated sulfuric acid in the sulfonation process, impregnation of 500 mmol titanium(IV isopropoxide and followed by alkyl silylation of n-octadecyltriclorosilane (OTS. The catalysts were characterized by X-ray diffraction (XRD, IR spectroscopy, nitrogen adsorption, and hydrophobicity. The catalytic activity of the catalysts has been examined in the liquid phase styrene oxidation by using aqueous hydrogen peroxide as oxidant. The catalytic study showed the alkyl silylation could enhance the catalytic activity of Ti-SO3H/CC-600(2.0. High catalytic activity and reusability of the o-Ti-SO3H/CC-600(2.0 were related to the modification of local environment of titanium active sites and the enhancement the hydrophobicity of catalyst particle by alkyl silylation. Copyright © 2017 BCREC GROUP. All rights reserved Received: 24th May 2016; Revised: 11st October 2016; Accepted: 18th October 2016 How to Cite: Nurhadi, M. (2017. Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 55-61 (doi:10.9767/bcrec.12.1.501.55-61 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.501.55-61

  17. Surface chemistry and catalytic properties of VO{sub X}/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    Energy Technology Data Exchange (ETDEWEB)

    González, J. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Chen, L.F., E-mail: lchen@ipn.mx [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Wang, J.A.; Manríquez, Ma.; Limas, R. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Schachat, P.; Navarrete, J. [Dirección de Investigación, Instituto Mexicano del Petróleo, Eje Lázaro Cárdenas 152, 07730 México D.F. (Mexico); Contreras, J.L. [Laboratorio de Catálisis y Polímeros, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-A, Av. San Pablo No. 180, 02200 México D.F. (Mexico)

    2016-08-30

    Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V{sub 2}O{sub 5}/Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H{sub 2}O{sub 2} as oxidant. ODS activity was found to be proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts, indicating that the surface vanadium pentoxide (V{sub 2}O{sub 5}) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V{sub 2}O{sub 5}) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V{sub 2}O{sub 5}/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  18. Structural changes of noble metal catalysts during ignition and extinction of the partial oxidation of methane studied by advanced QEXAFS techniques

    DEFF Research Database (Denmark)

    Grunwaldt, Jan-Dierk; Beier, M.; Kimmerle, B.

    2009-01-01

    The dynamics of the ignition and extinction of the catalytic partial oxidation (CPO) of methane to hydrogen and carbon monoxide over Pt-Rh/Al2O3 and Pt/Al2O3 were studied in the subsecond timescale using quick-EXAFS with a novel cam-driven X-ray monochromator employing Si(111) and Si(311) crystal...... of the CPO of methane and are complementing results from time-resolved infrared thermography and full field X-ray microscopy studies....

  19. The physicochemical properties and catalytic performance of carbon-covered alumina for oxidative dehydrogenation of ethylbenzene with CO2

    Science.gov (United States)

    Wang, Tehua; Chong, Siying; Wang, Tongtong; Lu, Huiyi; Ji, Min

    2018-01-01

    In order to correlate the physicochemical properties of carbon-covered alumina (CCA) materials with their catalytic performance for oxidative dehydrogenation of ethylbenzene with CO2 (CO2-ODEB), a series of CCA materials with diverse carbon contents (8.7-31.3 wt%) and pyrolysis temperatures (600-800 °C), which were synthesized via an impregnation method followed by pyrolysis, were applied. These catalytic materials were characterized by TGA, N2 physisorption, XRD, Raman spectroscopy and XPS techniques. It was found that the catalytic performance of these CCA materials highly depended on their physicochemical properties, and the optimum CCA catalyst exhibited much better catalytic stability than conventional hydroxyl carbon nanotubes. Below an optimum value of carbon content, the CCA catalyst preserved the main pore characteristics of the Al2O3 support and its catalytic activity increased with the carbon content. Excessive carbon loading resulted in significant textural alterations and thereby decreased both the ethylbenzene conversion and styrene selectivity. On the other hand, high pyrolysis temperature was detrimental to the ordered graphitic structure of the carbon species within the Al2O3 pore. The decreased ordered graphitic degree was found to be associated with the loss of the surface active carbonyl groups, consequently hampering the catalytic efficiency of the CCA catalyst.

  20. Study of propane partial oxidation on vanadium-containing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

  1. COMPARISON OF CATALYTIC ACTIVITIES BOTH FOR SELECTIVE OXIDATION AND DECOMPOSITION OF AMMONIA OVER Fe/HZβ CATALYST

    Directory of Open Access Journals (Sweden)

    YELİZ ÇETİN

    2016-11-01

    Full Text Available Ammonia is one of the syngas contaminants that must be removed before using the syngas downstream applications. The most promising hot-gas clean-up techniques of ammonia are selective catalytic oxidation (SCO and catalytic decomposition. In this study, the catalytic activities over Zeolite Hβ supported iron catalyst (Fe/HZβ were compared both for the two catalytic routes. For SCO experiments; temperature (300-550 °C, O2 (2000-6000 ppmv and (0-10% H2 concentrations were investigated with the presence of 800 ppm NH3 in each of the final gas mixture. In the second route, catalytic ammonia decomposition experiments were carried out with H2 in balance N2 (0-30% containing 800 ppm NH3 at 700°C and 800°C. In the SCO, NH3 conversions were increased with increasing reaction temperatures with the absence of H2 in the reaction mixture. With 10% H2, it was shown that NH3 conversions increased with decreasing the reaction temperature. This was interpreted as the competing H2 and NH3 oxidations over the catalyst. On the other hand, in the catalytic decomposition, thermodynamic equilibrium conversion of almost 100% was attained at both 700 and 800 °C. Upon H2 addition, all conversions decreased. The decrease in conversion seemed to be linear with inlet hydrogen concentration. Hydrogen was seen to inhibit ammonia decomposition reaction. It was shown that Fe/HZβ catalyst is better to use for catalytic decomposition of NH3 in syngas rather than SCO of NH3 in spite of higher reaction temperatures needed in the decomposition reaction.

  2. Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

    Science.gov (United States)

    Jin, Lei

    2011-12-01

    This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third

  3. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  4. Iridium nanoparticles with high catalytic activity in degradation of acid red-26: an oxidative approach.

    Science.gov (United States)

    Goel, Anjali; Lasyal, Rajni

    2016-12-01

    Nanocatalysis using metal nanoparticles constitutes one of the emerging technologies for destructive oxidation of organics such as dyes. This paper deals with the degradation of acid red-26 (AR-26), an azo dye by hexacyanoferrate (abbreviated as HCF) (III) using iridium nanoparticles. UV-vis spectroscopy has been employed to obtain the details of the oxidative degradation of the selected dye. The effect of various operational parameters such as HCF(III) concentration, pH, initial dye concentration, catalyst and temperature was investigated systematically at the λ max , 507 nm, of the reaction mixture. Degradation kinetics follows the first order kinetic model with respect to AR-26 and Ir nano concentrations, while with respect to the HCF(III) concentration reaction it follows first order kinetics at lower concentrations, tending towards zero order at higher concentrations. Thermodynamic parameters have been calculated by studying the reaction rate at four different temperatures. The UV-vis, high performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry (LC-MS) analysis of degradation products showed the formation of carboxylic acid and substituted carboxylic acids as major degradation products, which are simple and less hazardous compounds. The big advantage of the present method is the recovery and reuse of iridium nanoparticles. Moreover, turnover frequencies for each catalytic cycle have been determined, indicating the long life span of Ir nanoparticles. Thus, the finding is a novel and highly economical alternative for environmental safety against pollution by dyes, and extendable for other contaminants as well.

  5. Effective treatment of oily scum via catalytic wet persulfate oxidation process activated by Fe2.

    Science.gov (United States)

    Yuan, Xingzhong; Guan, Renpeng; Wu, Zhibin; Jiang, Longbo; Li, Yifu; Chen, Xiaohong; Zeng, Guangming

    2018-04-05

    Oily scum, a hazardous by-product of petroleum industry, need to be deposed urgently to reduce environmental risks. This paper introduces catalytic wet persulfate oxidation (CWPO) process in the treatment of oily scum to realize risk relief. Under the activation of heat and Fe 2+ , persulfate (PS) was decomposed into sulfate radicals and hydroxyl radicals, which played a major role on the degradation of petroleum hydrocarbons. The effects of wet air oxidation (WAO) and CWPO process on the degradation of oily scum were compared. In CWPO process, the total petroleum hydrocarbons (TPHs) content of oily scum was decreased from 92.63% to 16.75%, which was still up to 70.19% in WAO process. The degradation rate of TPHs in CWPO process was about 3.38 times higher than that in WAO process. The great performance of CWPO process was also confirmed by elemental analysis, which indicated that the C and H contents of oily scum were reduced significantly by CWPO process. These results indicated that CWPO process has high potential on the degradation of oily scum for environmental protection. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Protection of tobacco cells from oxidative copper toxicity by catalytically active metal-binding DNA oligomers.

    Science.gov (United States)

    Iwase, Junichiro; Furukawa, Hiroka; Hiramatsu, Takuya; Bouteau, François; Mancuso, Stefano; Tanaka, Kenichiro; Okazaki, Toshihiko; Kawano, Tomonori

    2014-03-01

    The impact of copper ions on the oxidative and calcium signal transductions, leading to cell death in plant cells, have been documented. Copper induces a series of biological and chemical reactions in plant cells including the oxidative burst reflecting the production of reactive oxygen species and the stimulation of calcium channel opening allowing a transient increase in cytosolic calcium concentrations. These early events, completed within a few minutes after the contact with copper, are known to trigger the development of cell death. The effects of DNA fragments with copper-binding motifs as novel plant cell-protecting agents were assessed using cell suspension cultures of transgenic tobacco (Nicotiana tabacum L., cell line BY-2) expressing the aequorin gene. The addition of GC-rich double-stranded DNA fragments, prior to the addition of copper ions, effectively blocked both the copper-induced calcium influx and cell death. In addition, the DNA-Cu complex examined was shown to possess superoxide-scavenging catalytic activity, suggesting that DNA-mediated protection of the cells from copper toxicity is due to the removal of superoxide. Lastly, a possible mechanism of DNA-Cu interaction and future applications of these DNA fragments in the protection of plant roots from metal toxicity or in aid of phyto-remediation processes are discussed.

  7. Metal-free catalytic oxidation of sulfides to sulfoxides with ammonium nitrate, ammonium hydrogen sulfate and ammonium bromide as catalyst

    OpenAIRE

    Ghorbani-Choghamarani, Arash; Zolfigol, Mohammad Ali; Ayazi-Nasrabadi, Roia

    2010-01-01

    A general and metal-free catalytic oxidation of aliphatic and aromatic sulfides to their corresponding sulfoxides via combination of ammonium nitrate (NH4NO3), supported ammonium hydrogen sulfate on silica gel (NH4HSO4-SiO2) and a catalytic amount of ammonium bromide (NH4Br) in the presence of wet SiO2 (50%, w/w) has been investigated. The reactions were carried out heterogeneously and selectively in short reaction times in CH2Cl2 at room temperature. This protocol is mild and efficient compa...

  8. Probing Hot Electron Flow Generated on Pt Nanoparticles with Au/TiO2 Schottky Diodes during Catalytic CO Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jeong Y.; Lee, Hyunjoo; Renzas, J. Russell; Zhang, Yawen; Somorjai, G.A.

    2008-05-01

    Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO{sub 2} diodes. Although Au/TiO{sub 2} diodes are not catalytically active, platinum nanoparticles on Au/TiO{sub 2} exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO{sub 2}. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (Tetradecyltrimethylammonium Bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O{sub 2} and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent, but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.

  9. TEMPO functionalized C{sub 60} fullerene deposited on gold surface for catalytic oxidation of selected alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Piotrowski, Piotr; Pawłowska, Joanna [University of Warsaw, Department of Chemistry (Poland); Sadło, Jarosław Grzegorz [Institute of Nuclear Chemistry and Technology (Poland); Bilewicz, Renata; Kaim, Andrzej, E-mail: akaim@chem.uw.edu.pl [University of Warsaw, Department of Chemistry (Poland)

    2017-05-15

    C{sub 60}TEMPO{sub 10} catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C{sub 60}TEMPO{sub 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{sub 2}/Fe{sup 3+} system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry.

  10. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry

    1998-12-31

    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

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

    International Nuclear Information System (INIS)

    Yigezu, Zerihun Demrew; Muthukumar, Karuppan

    2014-01-01

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

  12. Investigation of the coupled effects of temperature and partial pressure on catalytic growth of carbon nanotubes using a modified growth rate model

    Science.gov (United States)

    Zainal, M. T.; Mohd Yasin, M. F.; Wahid, M. A.

    2016-10-01

    An accurate modelling of catalytic growth of carbon nanotubes (CNTs) is needed to model the physics of carbon adsorption and diffusion into the catalyst surface along with the catalyst deactivation. The model should be able to provide a physical response towards the change of temperature and partial pressure. Though the effects of temperature and partial pressure on the growth rate has been studied individually, the coupled effects of the two parameters has yet to be emphasized. A modified growth rate model that unified the terms from previously developed models successfully captured the essential physics during the growth and provided physical response towards the change of temperature and partial pressure. The model validation was done against a chemical vapour deposition (CVD) experiment that employed acetylene and cobalt as the carbon source and the catalyst respectively where the modified model managed to predict the CNT terminal length more accurately compared to the standard model with 5% maximum error. A comprehensive parametric study on the effects of temperature and partial pressure on the growth rate and terminal length successfully reveals the minimum partial pressure of 5 Torr for a given operating condition below which the growth rate is significantly low regardless of any increase of temperature. Three regions of growth in the partial pressure-temperature domain are identified based on the magnitude of terminal length. The model can serve as a guideline for the determination and optimisation of the baseline operating conditions in future experiments on catalytic growth of CNT, with emphasis on the CVD and flame synthesis techniques.

  13. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. 1998 annual progress report

    International Nuclear Information System (INIS)

    Sen, A.

    1998-01-01

    'Toxic organics and polymers pose a serious threat to the environment, especially when they are present in aquatic systems. The objective of the research is the design of practical procedures for the removal and/or recycling of such pollutants by oxidation. This report summarizes the work performed in the first one and half years of a three year project. The authors had earlier described a catalytic system for the deep oxidation of toxic organics, such as benzene, phenol and substituted phenols, aliphatic and aromatic halogenated compounds, organophosphorus, and organosulfur compounds [1]. In this system, metallic palladium was found to catalyze the oxidation of the substrate by dioxygen in aqueous medium at 80--100 C in the presence of carbon monoxide. For all the substrates examined, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 h period. Because of a pressing need for new procedures for the destruction of chemical warfare agents, the authors have examined in detail the deep oxidation of appropriate model compounds containing phosphorus-carbon and sulfur-carbon bonds using the same catalytic system. The result is the first observation of the efficient catalytic oxidative cleavage of phosphorus-carbon and sulfur-carbon bonds under mild conditions, using dioxygen as the oxidant [2]. In addition to the achievements described above, they have unpublished results in several other areas. For example, they have investigated the possibility of using dihydrogen rather than carbon monoxide as a coreductant in the catalytic deep oxidation of substrates. Even more attractive from a practical standpoint is the possibility of using a mixture of carbon monoxide and dihydrogen (synthesis gas). Indeed, experiments indicated that it is possible to substitute carbon monoxide by dihydrogen or synthesis gas. Significantly, in the case of nitro compounds, the deep oxidation in fact proceeded

  14. Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

    Energy Technology Data Exchange (ETDEWEB)

    Musaev, Djamaladdin G [Chemistry, Emory University; Hill, Craig L [Chemistry, Emory University; Morokuma, Keiji [Chemistry, Emory University

    2014-10-28

    Abstract The central thrust of this integrated experimental and computational research program was to obtain an atomistic-level understanding of the structural and dynamic factors underlying the design of catalysts for water oxidation and selective reductant-free O2-based transformations. The focus was on oxidatively robust polyoxometalate (POM) complexes in which a catalytic active site interacts with proximal metal centers in a synergistic manner. Thirty five publications in high-impact journals arose from this grant. I. Developing an oxidatively and hydrolytically stable and fast water oxidation catalyst (WOC), a central need in the production of green fuels using water as a reductant, has proven particularly challenging. During this grant period we have designed and investigated several carbon-free, molecular (homogenous), oxidatively and hydrolytically stable WOCs, including the Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]·25H2O (1) and [Co4(H2O)2(α-PW9O34)2]10- (2). Although complex 1 is fast, oxidatively and hydrolytically stable WOC, Ru is neither abundant nor inexpensive. Therefore, development of a stable and fast carbon-free homogenous WOC, based on earth-abundant elements became our highest priority. In 2010, we reported the first such catalyst, complex 2. This complex is substantially faster than 1 and stable under homogeneous conditions. Recently, we have extended our efforts and reported a V2-analog of the complex 2, i.e. [Co4(H2O)2(α-VW9O34)2]10- (3), which shows an even greater stability and reactivity. We succeeded in: (a) immobilizing catalysts 1 and 2 on the surface of various electrodes, and (b) elucidating the mechanism of O2 formation and release from complex 1, as well as the Mn4O4L6 “cubane” cluster. We have shown that the direct O-O bond formation is the most likely pathway for O2 formation during water oxidation catalyzed by 1. II. Oxo transfer catalysts that contain two proximal and synergistically interacting redox active metal

  15. Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

    KAUST Repository

    Zhang, Xuming

    2015-01-01

    We studied the relative importance of the reduced field intensity and the background reaction temperature in the partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor. We obtained important mechanistic insight from studying high-temperature and low-pressure conditions with similar reduced field intensities. In the tested range of background temperatures (297 < T < 773 K), we found that the conversion of methane and oxygen depended on both the electron-induced chemistry and the thermo-chemistry, whereas the chemical pathways to the products were overall controlled by the thermo-chemistry at a given temperature. We also found that the thermo-chemistry enhanced the plasma-assisted partial oxidation process. Our findings expand our understanding of the plasma-assisted partial oxidation process and may be helpful in the design of cost-effective plasma reformers. © 2014 The Combustion Institute.

  16. One pot in situ growth of gold nanoparticles on amine-modified graphene oxide and their high catalytic properties

    Science.gov (United States)

    Ju, Yuyun; Li, Xi; Feng, Jie; Ma, Yanhua; Hu, Jing; Chen, Xingguo

    2014-10-01

    In this work, one pot strategy was proposed for in situ growth of Au nanoparticles (Au NPs) on the surface of amine-modified graphene oxide (GO@NH2) nanosheets. Au NPs were generated via an in situ reduction of Au3+ by Cu+ which was linked to the surface of GO@NH2 nanosheets through inorganic grafting. The initial Au NPs then served as seed for subsequent particle growth. The as-obtained GO@NH2-Au nanocomposites (GO@NH2-Au NCs) exhibited high catalytic activity for the degradation of 4-nitrophenol, which was a refractory pollutant that occur in industrial waste water. The catalytic efficiency was examined by turnover frequency (TOF). It was calculated to be 595 h-1, which was higher than that of other Au catalysts. Furthermore, the as-prepared catalyst showed high cycle stabilization during the catalytic reduction.

  17. Oriented Decoration in Metal-Functionalized Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Shijian Zhou

    2018-02-01

    Full Text Available Ordered mesoporous silicas (OMSs attract considerable attention due to their advanced structural properties. However, for the pristine silica materials, the inert property greatly inhibits their catalytic applications. Thus, to contribute to the versatile surface of OMSs, different metal active sites, including acidic/basic sites and redox sites, have been introduced into specific locations (mesoporous channels and framework of OMSs and the metal-functionalized ordered mesoporous silicas (MOMSs show great potential in the catalytic applications. In this review, we first present the categories of metal active sites. Then, the synthesized processes of MOMSs are thoroughly discussed, in which the metal active sites would be introduced with the assistance of organic groups into the specific locations of OMSs. In addition, the structural morphologies of OMSs are elaborated and the catalytic applications of MOMSs in the oxidation of aromatic compounds are illustrated in detail. Finally, the prospects for the future development in this field are proposed.

  18. Low-temperature catalytic oxidation of aldehyde mixtures using wood fly ash: kinetics, mechanism, and effect of ozone.

    Science.gov (United States)

    Kolar, Praveen; Kastner, James R

    2010-02-01

    Poultry rendering emissions contain volatile organic compounds (VOCs) that are nuisance, odorous, and smog and particulate matter precursors. Present treatment options, such as wet scrubbers, do not eliminate a significant fraction of the VOCs emitted including, 2-methylbutanal (2-MB), 3-methylbutanal, and hexanal. This research investigated the low-temperature (25-160 degrees C) catalytic oxidation of 2-MB and hexanal vapors in a differential, plug flow reactor using wood fly ash (WFA) as a catalyst and oxygen and ozone as oxidants. The oxidation rates of 2-MB and hexanal ranged between 3.0 and 3.5 x 10(-9)mol g(-1)s(-1) at 25 degrees C and the activation energies were 2.2 and 1.9 kcal mol(-1), respectively. The catalytic activity of WFA was comparable to other commercially available metal and metal oxide catalysts. We theorize that WFA catalyzed a free radical reaction in which 2-butanone and CO(2) were formed as end products of 2-MB oxidation, while CO(2), pentanal, and butanal were formed as end products of hexanal oxidation. When tested as a binary mixture at 25 and 160 degrees C, no inhibition was observed. Additionally, when ozone was tested as an oxidant at 160 degrees C, 100% removal was achieved within a 2-s reaction time. These results may be used to design catalytic oxidation processes for VOC removal at poultry rendering facilities and potentially replace energy and water intensive air pollution treatment technologies currently in use. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  19. Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO{sub 4} under Oxygen Atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kang Hyeok; Ko, Kwang Youn [Ajou University, Suwon (Korea, Republic of)

    2006-02-15

    KMnO{sub 4}/alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O{sub 2} atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO{sub 4}/alumina reagent acts as a catalytic oxidant under O{sub 2} atmosphere. Diphenyldiazomethane (Ph{sub 2}CN{sub 2}) is widely used for the protection of carboxylic acids by conversion to their diphenylmethyl (dpm) esters since dpm group can be easily deprotected by mild acidic condition or hydrogenolysis, especially in the field of b-lactams and peptides. Diphenyldiazomethane has been prepared by the oxidation of benzophenone hydrazone with reagents such as active manganese dioxide, mercuric oxide, peracetic acid, iodosobenzene diacetate or OXONE. However, some methods suffer from a disadvantage such as toxic nature of reagent, strong oxidative conditions or incompatibility with certain functional groups. For example, OXONE may not be employed for the in situ protection of carboxylic acid containing sulfide group due to the possibility of the concomitant oxidation of sulfide group.

  20. Excellent performance of Pt-C/TiO2 for methanol oxidation: Contribution of mesopores and partially coated carbon

    Science.gov (United States)

    Wu, Xinbing; Zhuang, Wei; Lu, Linghong; Li, Licheng; Zhu, Jiahua; Mu, Liwen; Li, Wei; Zhu, Yudan; Lu, Xiaohua

    2017-12-01

    Partial deposition of carbon onto mesoporous TiO2 (C/TiO2) were prepared as supporting substrate for Pt catalyst development. Carbon deposition is achieved by in-situ carbonization of furfuryl alcohol. The hybrid catalysts were characterized by XRD, Raman, SEM and TEM and exhibited outstanding catalytic activity and stability in methanol oxidation reaction. The heterogeneous carbon coated on mesoporous TiO2 fibers provided excellent electrical conductivity and strong interfacial interaction between TiO2 support and Pt metal nanoparticles. Methanol oxidation reaction results showed that the activity of Pt-C/TiO2 is 3.0 and 1.5 times higher than that of Pt-TiO2 and Pt-C, respectively. In addition, the Pt-C/TiO2 exhibited a 6.7 times enhanced stability compared with Pt-C after 2000 cycles. The synergistic effect of C/TiO2 is responsible for the enhanced activity of Pt-C/TiO2, and its excellent durability could be ascribed to the strong interfacial interaction between Pt nanoparticles and C/TiO2 support.

  1. Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO3, –MnO2, and –Mn2O3 Nanocomposites for Aerial Oxidation of Alcohols

    OpenAIRE

    Assal, Mohamed E.; Kuniyil, Mufsir; Shaik, Mohammed Rafi; Khan, Mujeeb; Al-Warthan, Abdulrahman; Siddiqui, Mohammed Rafiq H.; Adil, Syed Farooq

    2017-01-01

    Zinc oxide nanoparticles doped manganese carbonate catalysts [X% ZnOx–MnCO3] (where X = 0–7) were prepared via a facile and straightforward coprecipitation procedure, which upon different calcination treatments yields different manganese oxides, that is, [X% ZnOx–MnO2] and [X% ZnOx–Mn2O3]. A comparative catalytic study was conducted to evaluate the catalytic efficiency between carbonates and oxides for the selective oxidation of secondary alcohols to corresponding ketones using molecular oxyg...

  2. [Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

    Science.gov (United States)

    Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

    2013-06-01

    Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

  3. A comparative study of metal oxide and sulfate catalysts for selective catalytic reduction of NO with NH3.

    Science.gov (United States)

    Zhu, Lin; Zhong, Zhaoping; Yang, Han; Wang, Chunhua

    2017-05-01

    The properties and characteristics of metal oxide and sulfate catalysts with different active elements for selective catalytic reduction of NO with NH 3 were investigated. Cerium-based oxide catalyst showed the widest temperature window for NO x removal and manganese-based oxide catalyst exhibited the best catalytic performance at low temperature. For all the catalysts, the SCR activities at low temperature were directly related with the redox abilities of catalysts. The existence of sulfate groups inhibited the redox abilities of active species for sulfate catalysts compared with the metal oxide catalysts. The catalytic activities of CeWTi-S and MnWTi-S were seriously decreased in contrast to CeWTi-N and MnWTi-N. The temperature window of CuWTi-S was shifted toward higher temperature comparing with CuWTi-N. The FeWTi-N and FeWTi-S catalysts both showed high NO x conversion in the temperature range between 300°C and 400°C and N 2 O concentrations for iron-based samples were least among the same kind of catalysts. The abundance of acid sites and weak stability of surface sulfate groups for iron- and copper-based sulfate catalysts might be the main reasons accounting for the better NO x conversion in the medium-temperature range.

  4. Partial oxidation of methane to synthesis gas in a dual catalyst bed system combining irreducible oxide and metallic catalysts

    NARCIS (Netherlands)

    Zhu, J.J.; Mujeebur Rahuman, M.S.M.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    Operation of partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia (YSZ) at very high temperatures (¿900°C) slightly improves the selectivity to synthesis gas, which is caused by some activity of YSZ for steam and dry reforming of methane. LaCoO3 perovskite is not active in

  5. Direct Partial Oxidations Using Molecular Oxygen - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Richard [Univ. of New Mexico, Albuquerque, NM (United States)

    2017-11-01

    In 2006, Richard A. Kemp (University of New Mexico) and Karen I. Goldberg (University of Washington) formed a team and began to investigate new strategies to accomplish direct selective aerobic oxidations, with a particular emphasis on the epoxidation of propylene and higher olefins. This DOE-BES funded project was renewed twice and concluded after a no-cost extension earlier this year. Multiple novel strategies involving homogeneous catalyst systems were initiated and investigated during the award. Important fundamental understanding and insight concerning requirements for promotion of aerobic olefin epoxidation was generated. During the tenure of this project, new knowledge was generated concerning the synthesis, characterization and aerobic reactivity of metal hydrides and hydroxides. Key results describing synthetic strategies and optimization of the preparation of mononuclear late metal hydrides were published. The team reported the first example of O2 insertion into a Pd-H bond, a reaction which had been proposed in the literature but never previously observed. Our experimental investigation of the mechanism was later followed by computational work, and a description of what is now referred to as the Hydrogen Atom Abstraction (HAA) pathway for this reaction has been widely accepted in the community. After investigation of many other late metal hydrides, both experimentally and computationally, the team put together a chapter that included a description of key contributing factors that allow reaction by the HAA mechanism. A brief sampling of other classic papers from our project include hydrogenolysis reactions of late metal hydroxide and alkoxide complexes, the synthesis of nickel-hydrides, and the involvement of hemilabile ligands in promoting new reaction pathways.

  6. Nanocrystalline Mn-Mo-Ce Oxide Anode Doped Rare Earth Ce and Its Selective Electro-catalytic Performance

    Directory of Open Access Journals (Sweden)

    SHI Yan-hua

    2017-09-01

    Full Text Available The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO2, the OH- ion is preferentially absorbed, while Cl- absorption is depressed. OH- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn4+/Mn3+, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100 crystalline plane promotes OH- motion and the escape of newborn O2, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.

  7. Time resolved FTIR study of the catalytic CO oxidation under periodic variation of the reactant concentration

    Energy Technology Data Exchange (ETDEWEB)

    Kritzenberger, J.; Wokaun, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Oxidation of CO over palladium/zirconia catalyst obtained from an amorphous Pd{sub 25}Zr{sub 75} precursor was investigated by time resolved FTIR spectroscopy. Sine wave shaped modulation of the reactant concentration, i.e. variation of CO or O{sub 2} partial pressure, was used to induce variations of the IR signals of product (CO{sub 2}) and unconverted reactant (CO), which were detected in a multi-pass absorption cell. The phase shift {phi} between external perturbation and variation of the CO{sub 2} signal was examined in dependence on temperature (100{sup o}C{<=}T{<=}350{sup o}C) and modulation frequency (1.39x10{sup -4}Hz{<=}{omega}{<=}6.67x10{sup -2}Hz). From the phase shift values, a simple Eley-Rideal mechanism is excluded, and the rate limiting step of the Langmuir-Hinshelwood mechanism for the CO oxidation may be identified. Adsorption and possible surface movement of CO to the actual reaction site determine the rate of the CO oxidation on the palladium/zirconia catalyst used in our study. The introduction of an external perturbation is a first step towards the application of two-dimensional infrared spectroscopy to heterogeneous catalyzed reactions. (author) 3 figs., 4 refs.

  8. The influence of natural tocopherols during thermal oxidation of refined and partially hydrogenated soybean oils

    OpenAIRE

    Barrera-Arellano, D.; Dobarganes, M. C.; Steel, C. J.

    2005-01-01

    Samples of refined and partially hydrogenated soybean oils, with iodine values between 60 and 130, tocopherol-stripped or not by aluminium oxide treatment, were submitted to thermal oxidation, at 180 °C (during) for 10 hours. Samples were collected at 0, 2, 5, 8 and 10 hours, for the determination of dimers and polymers (degradation compounds) and tocopherols. The relation of iodine value to the formation of dimers and polymers and the role of originally present tocopherols in the ...

  9. Catalytic Oxidation of Vanillyl Alcohol Using FeMCM-41 Nanoporous Tubular Reactor

    Science.gov (United States)

    Elamathi, P.; Kolli, Murali Krishna; Chandrasekar, G.

    Iron containing nanoporous MCM-41 (FeMCM-41) with different Si/Fe ratios of 50, 100 and 150 was synthesized by hydrothermal synthesis process. The materials obtained from hydrothermal synthesis were characterized by various physico chemical techniques such as XRD, N2 adsorption, DR UV-vis, EPR and FTIR spectroscopy. XRD analyses of FeMCM-41 materials confirmed the presence of well-ordered crystalline structure. N2 isotherm of FeMCM-41 materials showed type IV adsorption isotherm. EPR and DR UV-vis analysis of FeMCM-41 samples indicates the presence of high tetrahedral coordination at the Si/Fe ratios of 100 and 150. The catalytic performance of FeMCM-41 nano tubular reactor was tested in the liquid phase oxidation of vanillyl alcohol into vanillin using H2O2 (50wt% in water). The reaction products were analyzed by gas chromatography in DB-5 capillary column with flame ionization detector. The products were confirmed by 1H NMR, 13C NMR and LC-Mass spectroscopy. The maximum conversion of vanillyl alcohol (85%) and selectivity towards vanillin (82%) were observed using the catalyst FeMCM-41(100) in 30min at 60∘C. The influence of reaction temperature, reaction time, reactants molar ratio, Si/Fe ratio and amount of catalyst were investigated.

  10. Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite.

    Science.gov (United States)

    Petitto, Carolina; Delahay, Gérard

    2018-03-01

    Nitrogen oxides (NO x : NO, NO 2 ) are a concern due to their adverse health effects. Diesel engine transport sector is the major emitter of NO x . The regulations have been strengthened and to comply with them, one of the two methods commonly used is the selective catalytic reduction of NO x by NH 3 (NH 3 -SCR), NH 3 being supplied by the in-situ hydrolysis of urea. Efficiency and durability of the catalyst for this process are highly required. Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C. In this study, very active catalysts for the NH 3 -SCR of NO x were prepared by using a silicoaluminophosphate commercial zeolite as copper host structure. Characterizations by X-ray diffraction (XRD), scanning electron microscopy (SEM) and temperature programmed desorption of ammonia (NH 3 -TPD) showed that this commercial zeolite was hydrothermally stable up to 850°C and, was able to retain some structural properties up to 950°C. After hydrothermal treatment at 850°C, the NO x reduction efficiency into NH 3 -SCR depends on the copper content. The catalyst with a copper content of 1.25wt.% was the most active. The difference in activity was much more important when using NO than the fast NO/NO 2 reaction mixture. Copyright © 2017. Published by Elsevier B.V.

  11. Supported noble metal catalysts in the catalytic wet air oxidation of industrial wastewaters and sewage sludges.

    Science.gov (United States)

    Besson, M; Descorme, C; Bernardi, M; Gallezot, P; di Gregorio, F; Grosjean, N; Minh, D Pham; Pintar, A

    2010-12-01

    This paper reviews some catalytic wet air oxidation (CWAO) investigations of industrial wastewaters over platinum and ruthenium catalysts supported on TiO2 and ZrO2 formulated to be active and resistant to leaching, with particular focus on the stability of the catalyst. Catalyst recycling experiments were performed in batch reactors and long-term stability tests were conducted in trickle-bed reactors. The catalyst did not leach upon treatment of Kraft bleaching plant and olive oil mill effluents, and could be either recycled or used for long periods of time in continuous reactors. Conversely, these catalysts were rapidly leached when used to treat effluents from the production of polymeric membranes containing N,N-dimethylformamide. The intermediate formation of amines, such as dimethylamine and methylamine with a high complexing capacity for the metal, was shown to be responsible for the metal leaching. These heterogeneous catalysts also deactivated upon CWAO of sewage sludges due to the adsorption of the solid organic matter. Pre-sonication of the sludge to disintegrate the flocs and improve solubility was inefficient.

  12. Environmental and economic evaluation of selective non-catalytic reduction of nitrogen oxides

    Science.gov (United States)

    Parchevskii, V. M.; Shchederkina, T. E.; Proshina, A. O.

    2017-11-01

    There are two groups of atmosphere protecting measures: technology (primary) and treatment (secondary). When burning high-calorie low-volatile brands of coals in the furnaces with liquid slag removal to achieve emission standards required joint use of these two methods, for example, staged combustion and selective non-catalytic reduction recovery (SNCR). For the economically intelligent combination of these two methods it is necessary to have information not only about the environmental performance of each method, but also the operating costs per unit of reduced emission. The authors of this report are made an environmental-economic analysis of SNCR on boiler Π-50P Kashirskaya power station. The obtained results about the dependence of costs from the load of the boiler and the mass emissions of nitrogen oxides then approximates into empirical formulas, is named as environmental and economic characteristics, which is suitable for downloading into controllers and other control devices for subsequent implementation of optimal control of emissions to ensure compliance with environmental regulations at the lowest cost at any load of the boiler.

  13. Investigation into catalytic properties of the second group metal molybdates in acrolein oxidation

    International Nuclear Information System (INIS)

    Yakubovich, M.N.; Gorochovatskij, Ya.B.; Alchazov, T.G.; Adzhamov, K.Yu.

    1976-01-01

    The catalytic properties are investigated of magnesium, calcium, strontium, zinc, cadmium, and barium molybdates. Temperature dependence of catalysts activity is studied. At temperature over 370 deg C the activity becomes higher in the series ZnMoO 4 -CaMoO 4 -MgMoO 4 -SrMoO 4 . A sharp fall in the activity is observed for BaMoO 4 , and CdMoO 4 . SrMoO 4 is the most active catalyst. The activity series have been made up with respect to the formation of acrylic acid: MgMoO 4 >ZnMoO 4 >CaMoO 4 , and also with respect to the formation of the deep oxidation products: SrMoO 4 >CaMoO 4 >MgMoO 4 >ZnMoO 4 . The dependence of selectivity with respect to the formation of acrylic acid and the sum of the acids on temperature is provided

  14. Hierarchical nano-on-micro copper with enhanced catalytic activity towards electro-oxidation of hydrazine

    Science.gov (United States)

    Yan, Xiaodong; Liu, Yuan; Scheel, Kyle R.; Li, Yong; Yu, Yunhua; Yang, Xiaoping; Peng, Zhonghua

    2018-01-01

    The electrochemical properties of catalyst materials are highly dependent on the materials structure and architecture. Herein, nano-on-micro Cu electrodes are fabricated by growing Cu microcrystals on Ni foam substrate, followed by introducing Cu nanocrystals onto the surface of the Cu microcrystals. The introduction of Cu nanocrystals onto the surface of Cu microcrystals is shown to dramatically increase the electrochemically active surface area and thus significantly enhances the catalytic activity of the catalyst electrode towards electro-oxidation of hydrazine. The onset potential (-1.04 V vs. Ag/AgCl) of the nano-on-micro Cu electrode is lower than those of the reported Cu-based catalysts under similar testing conditions, and a current density of 16 mA·cm-2, which is 2 times that of the microsized Cu electrode, is achieved at a potential of -0.95 V vs. Ag/AgCl. Moreover, the nano-on-micro Cu electrode demonstrates good long-term stability.

  15. [In situ diffuse reflectance FTIR spectroscopy characterization of titanium silicalite-1 catalytic oxidization of styrene].

    Science.gov (United States)

    Zhang, Ping; Wang, Le-fu; Chen, Yong-heng

    2007-05-01

    The Stability of framework of titanium silicalite-1 (TS-1) was investigated by high temperature diffuse reflectance FT-IR spectroscopy (DRIFTS), and the results showed that the 960 cm(-1) peak belonging to Ti-framework was stabilized at 673 K, but the two peaks belonging to framework shifted to lower frequencies by about 13 cm(-1) at 673 K. The effect on the framework after H2O2 adsorption was discussed. The results showed that the 960 cm(-1) peak lowered and shifted to high frequencies by about 11 cm(-1), but it recovered with vacuum or heating up. It was suggested that the 960 cm(-1) peak characterizes Ti==O, and this explained why the 960 cm(-1) peak shifted to high frequencies well. TS-1 catalytic oxidization of styrene was investigated by in situ DRIFTS. The reaction process was detected and phenyl aldehyde was the main product. Based on in situ analysis, it was proposed that H2O2 was adsorbed on Ti in framework of TS-1 to form active center.

  16. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A

    2014-04-08

    A multi-stage selective catalytic reduction (SCR) unit (32) provides efficient reduction of NOx and other pollutants from about 50-550.degree. C. in a power plant (19). Hydrogen (24) and ammonia (29) are variably supplied to the SCR unit depending on temperature. An upstream portion (34) of the SCR unit catalyzes NOx+NH.sub.3 reactions above about 200.degree. C. A downstream portion (36) catalyzes NOx+H.sub.2 reactions below about 260.degree. C., and catalyzes oxidation of NH.sub.3, CO, and VOCs with oxygen in the exhaust above about 200.degree. C., efficiently removing NOx and other pollutants over a range of conditions with low slippage of NH.sub.3. An ammonia synthesis unit (28) may be connected to the SCR unit to provide NH.sub.3 as needed, avoiding transport and storage of ammonia or urea at the site. A carbonaceous gasification plant (18) on site may supply hydrogen and nitrogen to the ammonia synthesis unit, and hydrogen to the SCR unit.

  17. Removal of Selected Heavy Metals from Green Mussel via Catalytic Oxidation

    International Nuclear Information System (INIS)

    Faizuan Abdullah; Abdull Rahim Mohd Yusoff; Wan Azelee Wan Abu Bakar; Razali Ismail; Dwi Priya Hadiyanto

    2014-01-01

    Perna viridis or green mussel is a potentially an important aquaculture product along the South Coast of Peninsular Malaysia especially Johor Straits. As the coastal population increases at tremendous rate, there was significant effect of land use changes on marine communities especially green mussel, as the heavy metals input to the coastal area also increase because of anthropogenic activities. Heavy metals content in the green mussel exceeded the Malaysian Food Regulations (1985) and EU Food Regulations (EC No: 1881/ 2006). Sampling was done at Johor Straits from Danga to Pendas coastal area for green mussel samples. This research introduces a catalytic oxidative technique for demetallisation in green mussel using edible oxidants such as peracetic acid (PAA) enhanced with alumina beads supported CuO, Fe 2 O 3 , and ZnO catalysts. The lethal dose of LD 50 to rats of PAA is 1540 mg kg -1 was verified by National Institute of Safety and Health, United State of America. The best calcination temperature for the catalysts was at 1000 degree Celsius as shown in the X-Ray Diffraction (XRD), Nitrogen Adsorption (BET surface area) and Field Emission Scanning Electron Microscopy (FESEM) analyses. The demetallisation process in green mussel was done successfully using only 100 mgL -1 PAA and catalyzed with Fe 2 O 3 / Al 2 O 3 for up to 90 % mercury (Hg) removal. Using PAA with only 1 hour of reaction time, at room temperature (30-35 degree Celsius), pH 5-6 and salinity of 25-28 ppt, 90 % lead (Pb) was removed from life mussel without catalyst. These findings have a great prospect for developing an efficient and practical method for post-harvesting heavy metals removal in green mussel. (author)

  18. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  19. Eco-friendly synthesis and characterization of Ni-Si nanoparticles mixed oxides as catalyst for partial oxidation of methane

    International Nuclear Information System (INIS)

    Fakhroueian, Z.; Farzaneh, F.

    2009-01-01

    The nanoparticles of Ni-Si mixed oxides were prepared by co-precipitation method using nickel nitrate; Ni(NO 3 ) 2 6H 2 O and tetraethyl orthosilicate. The products were characterized by X-ray diffraction, transmission electron microscopy, and hydrogen temperature program reduction (H 2 -TPR). The results revealed that Ni-Si mixed oxides particles were obtained with average particle size 1-2 nm. The Ni-Si nanoparticles mixed oxides successfully catalyzed the partial oxidation of methane to hydrogen and carbon monoxide (Syn gas) using a fixed-bed reactor with about 92% activity and high selectivity. No coke formation and deactivation of catalyst were observed during the course of reaction. Particularly significant is the similar reactivity of this catalyst with that of Ni-Ce-Zr mixed oxides

  20. Synergism between anodic oxidation with diamond anodes and heterogeneous catalytic photolysis for the treatment of pharmaceutical pollutants

    Directory of Open Access Journals (Sweden)

    Juan M. Peralta-Hernández

    2016-03-01

    Full Text Available The mineralization of diclofenac and acetaminophen has been studied by single anodic oxidation with boron-doped diamond (AO-BDD using an undivided electrolysis cell, by single heterogeneous catalytic photolysis with titanium dioxide (HCP-TiO2 and by the combination of both advanced oxidation processes. The results show that mineralization can be obtained with either single technology. The type of functional groups of the pollutant does not influence the results of the single AO-BDD process, but it has a significant influence on the results obtained with HCP-TiO2. A clear synergistic effect appears when both processes are combined showing improvements in the oxidation rate of more than 50% for diclofenac and nearly 200% for acetaminophen at the highest current exerted. Results obtained are explained in terms of the production of oxidants on the surface of BDD (primarily peroxodisulfate and the later homogeneous catalytic light decomposition of these oxidants in the bulk. This mechanism is consistent with the larger improvement observed at higher current densities, for which the production of oxidants is promoted.

  1. A Broad Spectrum Catalytic System for Removal of Toxic Organics from Water by Deep Oxidation - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sen, Ayusman

    2000-12-01

    A most pressing need for the DOE environmental management program is the removal of toxic organic compounds present in groundwater and soil at specific DOE sites. While several remediation procedures have been proposed, they suffer from one or more drawbacks. The objective of the present research was to develop new catalytic procedures for the removal of toxic organic compounds from the environment through their deep oxidation to harmless products. In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of toxic organic compounds by dioxygen at 80-90 C in the presence of carbon monoxide or dihydrogen. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, nitro and halo organics, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 hour period. For substrates susceptible to hydrogenation, the conversions were generally high with dihydrogen than with carbon monoxide. It is clear from the results obtained that we have discovered an exceptionally versatile catalytic system for the deep oxidation of toxic organic compounds in water. This system possesses several attractive features not found simultaneously in other reported systems. These are (a) the ability to directly utilize dioxygen as the oxidant, (b) the ability to carry out the deep oxidation of a particularly wide range of functional organics, and (c) the ease of recovery of the catalyst by simple filtration.

  2. Enhanced catalytic and dopamine sensing properties of electrochemically reduced conducting polymer nanocomposite doped with pure graphene oxide.

    Science.gov (United States)

    Wang, Wenting; Xu, Guiyun; Cui, Xinyan Tracy; Sheng, Ge; Luo, Xiliang

    2014-08-15

    Significantly enhanced catalytic activity of a nanocomposite composed of conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) doped with graphene oxide (GO) was achieved through a simple electrochemical reduction process. The nanocomposite (PEDOT/GO) was electrodeposited on an electrode and followed by electrochemical reduction, and the obtained reduced nanocomposite (PEDOT/RGO) modified electrode exhibited lowered electrochemical impedance and excellent electrocatalytic activity towards the oxidation of dopamine. Based on the excellent catalytic property of PEDOT/RGO, an electrochemical sensor capable of sensitive and selective detection of DA was developed. The fabricated sensor can detect DA in a wide linear range from 0.1 to 175μM, with a detection limit of 39nM, and it is free from common interferences such as uric acid and ascorbic acid. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Fabrication of ammonium perchlorate/copper-chromium oxides core-shell nanocomposites for catalytic thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Eslami, Abbas, E-mail: eslami@umz.ac.ir [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Juibari, Nafise Modanlou [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Hosseini, Seyed Ghorban [Department of Chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3454, Tehran (Iran, Islamic Republic of)

    2016-09-15

    The ammonium perchlorate/Cu(II)-Cr(III)-oxides(AP/Cu-Cr-O) core-shell nanocomposites were in-situ prepared by deposition of copper and chromium oxides on suspended ammonium perchlorate particles in ethyl acetate as solvent. The results of differential scanning calorimetery (DSC) and thermal gravimetric analysis (TGA) experiments showed that the nanocomposites have excellent catalytic effect on the thermal decomposition of AP, so that the released heat increases up to about 3-fold over initial values, changing from 450 J/g for pure AP to 1510 J/g for most appropriate mixture. For better comparison, single metal oxide/AP core-shell nanocomposite have also been prepared and the results showed that they have less catalytic effect respect to mixed metal oxides system. Scanning electron microscopy (SEM) results revealed homogenous deposition of nanoparticles on the surface of AP and fabrication of core-shell structures. The kinetic parameters of thermal decomposition of both pure AP and AP/Cu-Cr-O samples have been calculated by Kissinger method and the results showed that the values of pre-exponential factor and activation energy are higher for AP/Cu-Cr-O nanocomposite. The better catalytic effect of Cu-Cr-O nanocomposites is probably attributed to the synergistic effect between Cu{sup 2+} and Cr{sup 3+} in the nanocomposites, smaller particle size and more crystal defect. - Highlights: • The Cu-Cr-O nanoparticles were synthesized by chemical liquid deposition method. • Then, the AP/Cu-Cr-O core-shell nanocomposites were prepared. • The core-shell samples showed high catalytic activity for AP decomposition. • Thermal decomposition of samples occurs at lower temperature range.

  4. Fabrication of ammonium perchlorate/copper-chromium oxides core-shell nanocomposites for catalytic thermal decomposition of ammonium perchlorate

    International Nuclear Information System (INIS)

    Eslami, Abbas; Juibari, Nafise Modanlou; Hosseini, Seyed Ghorban

    2016-01-01

    The ammonium perchlorate/Cu(II)-Cr(III)-oxides(AP/Cu-Cr-O) core-shell nanocomposites were in-situ prepared by deposition of copper and chromium oxides on suspended ammonium perchlorate particles in ethyl acetate as solvent. The results of differential scanning calorimetery (DSC) and thermal gravimetric analysis (TGA) experiments showed that the nanocomposites have excellent catalytic effect on the thermal decomposition of AP, so that the released heat increases up to about 3-fold over initial values, changing from 450 J/g for pure AP to 1510 J/g for most appropriate mixture. For better comparison, single metal oxide/AP core-shell nanocomposite have also been prepared and the results showed that they have less catalytic effect respect to mixed metal oxides system. Scanning electron microscopy (SEM) results revealed homogenous deposition of nanoparticles on the surface of AP and fabrication of core-shell structures. The kinetic parameters of thermal decomposition of both pure AP and AP/Cu-Cr-O samples have been calculated by Kissinger method and the results showed that the values of pre-exponential factor and activation energy are higher for AP/Cu-Cr-O nanocomposite. The better catalytic effect of Cu-Cr-O nanocomposites is probably attributed to the synergistic effect between Cu 2+ and Cr 3+ in the nanocomposites, smaller particle size and more crystal defect. - Highlights: • The Cu-Cr-O nanoparticles were synthesized by chemical liquid deposition method. • Then, the AP/Cu-Cr-O core-shell nanocomposites were prepared. • The core-shell samples showed high catalytic activity for AP decomposition. • Thermal decomposition of samples occurs at lower temperature range.

  5. N2O Catalytic Decomposition - Effect of Pelleting Pressure on Activity of Co-Mn-Al Mixed Oxide Catalyst

    Czech Academy of Sciences Publication Activity Database

    Galejová, K.; Obalová, L.; Jirátová, Květa; Pacultová, K.; Kovanda, F.

    2009-01-01

    Roč. 63, č. 2 (2009), s. 172-179 ISSN 0366-6352. [International Conference of the Slovak-Society-of-Chemical-Engineering /35./. Tatranske Matliare, 26.05.2008-30.05.2008] R&D Projects: GA ČR GA104/07/1400 Institutional research plan: CEZ:AV0Z40720504 Keywords : pelleting pressure * nitrous oxide * catalytic decomposition Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.791, year: 2009

  6. Electrochemical behaviour of metal hexacyanoferrate converted to metal hydroxide films immobilized on indium tin oxide electrodes-Catalytic ability towards alcohol oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Ganesh, V.; Latha Maheswari, D.; Berchmans, Sheela

    2011-01-01

    Graphical abstract: - Abstract: In this work, we demonstrate a simple method to modify indium tin oxide (ITO) electrodes in order to perform electro-catalytic oxidation of alcohols in alkaline medium. Metal hexacyanoferrate (MHCF) films such as nickel hexacyanoferrate (NiHCF) and copper hexacyanoferrate (CuHCF) were successfully immobilized on ITO electrodes using an electrochemical method. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the structural and morphological aspects of MHCF films. Cyclic voltammetry (CV) was used to study the redox properties and to determine the surface coverage of these films on ITO electrodes. Electrochemical potential cycling was carried out in alkaline medium in order to alter the chemical structure of these films and convert to their corresponding metal hydroxide films. SEM and XPS were performed to analyze the structure and morphology of metal hydroxide modified electrodes. Electro-catalytic oxidation ability of these films towards methanol and ethanol in alkaline medium was investigated using CV. From these studies we found that metal hydroxide modified electrodes show a better catalytic performance and good stability for methanol oxidation along with the alleviation of CO poisoning effect. We have obtained an anodic oxidation current density of ∼82 mA cm -2 for methanol oxidation, which is at least 10 fold higher than that of any metal hydroxide modified electrodes reported till date. The onset potential for methanol oxidation is lowered by ∼200 mV compared to other chemically modified electrodes reported. A plausible mechanism was proposed for the alcohol oxidation based on the redox properties of these modified electrodes. The methodology adapted in this work does not contain costlier noble metals like platinum and ruthenium and is economically viable.

  7. Enhanced catalytic stability of lipase immobilized on oxidized and disulfide-rich eggshell membrane for esters hydrolysis and transesterification.

    Science.gov (United States)

    Jiang, Chenyu; Cheng, Chuanchuan; Hao, Mei; Wang, Hongbin; Wang, Ziying; Shen, Cai; Cheong, Ling-Zhi

    2017-12-01

    Eggshell membrane (ESM) is an industrial waste that is available in abundance from food industry. Present study investigated the physicochemical properties of oxidized ESM and compared the efficiency of ESM and oxidized ESM as carrier for Burkholderia cepacia lipase (BCL) used in esters hydrolysis and transesterification. Following oxidation treatment, FTIR analysis and Ellman's assay showed amino acid cysteine in ESM was oxidized to form disulfide bond-containing cystine. In addition, AFM analysis showed ESM which exhibited a highly porous filamentous structure appeared to be coalesce following oxidation treatment. Oxidized ESM also showed reduced porosity (38.67%) in comparison to native ESM (51.65%). BCL were successfully immobilized on oxidized ESM through carrier activation method (enzyme loading of 5.01mg protein/g oxidized ESM). These immobilized lipase demonstrated significantly (Ptransesterification (7.83±0.05) activity for at least 10 consecutive runs. Enhanced catalytic stability of BCL immobilized on oxidized ESM might be due to stabilization of the protein structure in oxidized ESM by disulfide bonds which helped formation of a stable bonding with BCL. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone

    Directory of Open Access Journals (Sweden)

    Ilhem Rekkab-Hammoumraoui

    2018-01-01

    Full Text Available A series of metal-loaded (Ru, Pt, Co alumina catalysts were evaluated for the catalytic oxidation of cyclohexane using tertbutylhydroperoxide (TBHP as oxidant and acetonitrile or acetic acid as solvent. These materials were prepared by the impregnation method and then characterized by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES, H2 chemisorption, Fourier Transformed Infrared Spectroscopy (FTIR, High-Resolution Transmission Electron Microscopy (HRTEM, and X-ray Diffraction (XRD. All the prepared materials acted as efficient catalysts. Among them, Ru/Al2O3 was found to have the best catalytic activity with enhanced cyclohexane conversion of 36 %, selectivity to cyclohexanol and cyclohexanone of 96 % (57.6 mmol, and cyclohexane turnover frequency (TOF of 288 h-1. Copyright © 2018 BCREC Group. All rights reserved Received: 26th May 2017; Revised: 17th July 2017; Accepted: 18th July 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Rekkab-Hammoumraoui, I., Choukchou-Braham, A. (2018. Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone. Bulletin of Chemical Reaction Engineering & Catalysis, 13(1: 24-36 (doi:10.9767/bcrec.13.1.1226.24-35

  9. A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature.

    Science.gov (United States)

    Deng, Dehui; Chen, Xiaoqi; Yu, Liang; Wu, Xing; Liu, Qingfei; Liu, Yun; Yang, Huaixin; Tian, Huanfang; Hu, Yongfeng; Du, Peipei; Si, Rui; Wang, Junhu; Cui, Xiaoju; Li, Haobo; Xiao, Jianping; Xu, Tao; Deng, Jiao; Yang, Fan; Duchesne, Paul N; Zhang, Peng; Zhou, Jigang; Sun, Litao; Li, Jianqi; Pan, Xiulian; Bao, Xinhe

    2015-12-01

    Coordinatively unsaturated (CUS) iron sites are highly active in catalytic oxidation reactions; however, maintaining the CUS structure of iron during heterogeneous catalytic reactions is a great challenge. Here, we report a strategy to stabilize single-atom CUS iron sites by embedding highly dispersed FeN4 centers in the graphene matrix. The atomic structure of FeN4 centers in graphene was revealed for the first time by combining high-resolution transmission electron microscopy/high-angle annular dark-field scanning transmission electron microscopy with low-temperature scanning tunneling microscopy. These confined single-atom iron sites exhibit high performance in the direct catalytic oxidation of benzene to phenol at room temperature, with a conversion of 23.4% and a yield of 18.7%, and can even proceed efficiently at 0°C with a phenol yield of 8.3% after 24 hours. Both experimental measurements and density functional theory calculations indicate that the formation of the Fe═O intermediate structure is a key step to promoting the conversion of benzene to phenol. These findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis and electrocatalysis.

  10. Oxygen partial pressure: a key to alloying and discovery in metal oxide--metal eutectic systems

    International Nuclear Information System (INIS)

    Holder, J.D.; Clark, G.W.; Oliver, B.F.

    1978-01-01

    Control of oxygen partial pressure is essential in the directional solidification of oxide--metal eutectic composites by techniques involving gas-solid and gas-liquid interactions. The existence of end components in the eutectic composite is Po 2 sensitive as are melt stoichiometry, solid phase compositions, and vapor losses due to oxidation-volatilization. Simple criteria are postulated which can aid the experimentalist in selecting the proper gas mixture for oxide--metal eutectic composite growth. The Cr 2 O 3 --Mo--Cr systems was used to verify certain aspects of the proposed criteria

  11. Development of a novel reactor concept for the partial oxidation of methane to syngas

    NARCIS (Netherlands)

    Smit, J.; van Sint Annaland, M.; Kuipers, J.A.M.

    2004-01-01

    The gas-to-liquid process, consisting of the partial oxidation of methane (POM) followed by the Fischer-Tropsch reaction, is a promising alternative to conventional oil processing for the production of liquid fuels. The cost of a conventional POM process is mainly determined by cryogenic air

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

    Czech Academy of Sciences Publication Activity Database

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

    2014-01-01

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

  13. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; van Sint Annaland, M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal

  14. Thermodynamic analysis of the partial oxidation of coke oven gas for indirect reduction of iron oxides in a blast furnace

    International Nuclear Information System (INIS)

    Chen, Wei-Hsin; Hsu, Chih-Liang; Du, Shan-Wen

    2015-01-01

    The partial oxidation of a COG (coke oven gas) in a blast furnace is examined in this work using thermodynamic analysis. LTIR and HTIR (Low-temperature and high-temperature indirect reduction) of iron oxides in a blast furnace are also studied. The influences of the reaction temperature, M/H (methane-to-hematite) ratio, and O/F (oxygen-to-fuel) ratio on CH 4 conversion and iron oxide reduction are examined. Within the investigated ranges of the parameters, a higher reaction temperature is conducive to CH 4 conversion, while at least 97.64% of Fe 2 O 3 is reduced. In LTIR, Fe 3 O 4 is the prime product, with a high level of solid carbon formation. The entire LTIR reaction is characterized by exothermic behavior, so that no additional heat is required to trigger COG partial oxidation and IR. In HTIR, increasing the reaction temperature facilitates CO-based IR and suppresses H 2 -based IR. A higher temperature produces more Fe, so as to enhance the iron oxide reduction reactions; meanwhile, the FeO reduction is governed by H 2 and CH 4 . When the reaction temperature is higher than 800 °C and the M/H ratio is lower than unity, a heat supply is required to drive HTIR. The O/F ratio in LTIR and HTIR should be controlled below 2 to retard carbon formation and drive iron oxide reduction. - Highlights: • Direct partial oxidation of coke oven gas in blast furnace is analyzed thermodynamically. • A higher reaction temperature is conducive to CH 4 conversion and syngas production. • At least 97.64% of Fe 2 O 3 is converted. • The low-temperature indirect reduction is characterized by exothermic behavior. • The oxygen-to-fuel molar ratio in indirect reduction should be controlled below 2

  15. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  16. Reduced graphene oxide wrapped Fe3O4-Co3O4 yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals

    Science.gov (United States)

    Zhang, Lishu; Yang, Xijia; Han, Erfen; Zhao, Lijun; Lian, Jianshe

    2017-02-01

    In this work, we designed and synthesized a high performance catalyst of reduced graphene oxide (RGO) wrapped Fe3O4-Co3O4 (RGO/Fe3O4-Co3O4) yolk-shell nanostructures for advanced catalytic oxidation based on sulfate radicals. The synergistic catalytic action of the RGO/Fe3O4-Co3O4 yolk-shell nanostructures activate the peroxymonosulfate (PMS) to produce sulfate radicals (SO4rad -) for organic dyes degradation, and the Orange II can be almost completely degradated in 5 min. Meanwhile the RGO wrapping prevents the loss of cobalt in the catalytic process, and the RGO/Fe3O4-Co3O4 can be recycled after catalyzed reaction due to the presence of magnetic iron core. What's more, it can maintain almost the same high catalytic activity even after 10 cycles through repeated NaBH4 reduction treatment. Hence, RGO/Fe3O4-Co3O4 yolk-shell nanostructures possess a great opportunity to become a promising candidate for waste water treatment in industry.

  17. Enhanced adsorption and catalytic oxidation of ciprofloxacin by an Ag/AgCl@N-doped activated carbon composite

    Science.gov (United States)

    Nekouei, Farzin; Nekouei, Shahram; Noorizadeh, Hossein

    2018-03-01

    In this study, we synthesized a new nanocomposite catalyst comprising Ag/AgCl@N-doped activated carbon (Ag/AgCl@N-AC) and demonstrated its high efficiency during the enhanced adsorptive removal and catalytic oxidation of ciprofloxacin (CIP) with peroxymonosulfate (PMS) and persulfate (PS) as oxidants in aqueous solution. The efficiency of the new nanocomposite was compared with those of both pristine AC and N-AC under the same conditions. Furthermore, the effects of oxidants on the catalytic oxidation of CIP were assessed using PMS and PS. We found that the degradation efficiency of CIP with Ag/AgCl@N-AC was higher when using PS as an oxidant, whereas the use of PMS obtained relatively better results with both AC and N-AC. The adsorption processes for AC, N-AC, and Ag/AgCl@N-AC were dominated not only by electrostatic attraction but also by π-π interactions, which had higher impacts on the adsorption processes than the specific surface area.

  18. Performance comparison between partial oxidation and methane steam for SOFC micro-CHP systems

    DEFF Research Database (Denmark)

    Liso, Vincenzo; Olesen, Anders Christian; Nielsen, Mads Pagh

    2011-01-01

    The aim of this research work is to describe in qualitative and quantitative form the performance of a micro Combined Heat and Power system for residential application based on Solid Oxide Fuel Cell fueled by natural gas with two different types of pre-reforming systems, namely Steam Reforming...... and Partial Oxidation and recirculation of anode and cathode gas. The comparative analysis among the different configurations will lead us to conclude that maximum efficiency is achieved when cathode and anode gas recirculation are used along with steam methane reforming. Further Steam Methane Reforming...... process produces a higher electrical system efficiency compared to Partial oxidation reforming process. Efficiency is affected when running the system in part load mode mainly due to heat loss, additional natural gas supplied to the burner to satisfy the required heat demand inside the system, and ejector...

  19. Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of catalytic ultrasound oxidation and membrane bioreactor.

    Science.gov (United States)

    Jia, Shengyong; Han, Hongjun; Zhuang, Haifeng; Xu, Peng; Hou, Baolin

    2015-01-01

    Laboratorial scale experiments were conducted to investigate a novel system integrating catalytic ultrasound oxidation (CUO) with membrane bioreactor (CUO-MBR) on advanced treatment of biologically pretreated coal gasification wastewater. Results indicated that CUO with catalyst of FeOx/SBAC (sewage sludge based activated carbon (SBAC) which loaded Fe oxides) represented high efficiencies in eliminating TOC as well as improving the biodegradability. The integrated CUO-MBR system with low energy intensity and high frequency was more effective in eliminating COD, BOD5, TOC and reducing transmembrane pressure than either conventional MBR or ultrasound oxidation integrated MBR. The enhanced hydroxyl radical oxidation, facilitation of substrate diffusion and improvement of cell enzyme secretion were the mechanisms for CUO-MBR performance. Therefore, the integrated CUO-MBR was the promising technology for advanced treatment in engineering applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions

    KAUST Repository

    Feng, Zhenxing

    2016-05-05

    δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1–ySry)2CoO4±δ/La1–xSrxCo0.2Fe0.8O3−δ. Sr enrichment in many electrocatalysts, such as La1–xSrxMO3−δ (M = Cr, Co, Mn, or Co and Fe) and Sm1–xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst’s activity while maintaining stability to design efficient, cost-effective electrocatalysts.

  1. Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

    Science.gov (United States)

    Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

    2017-07-03

    Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

  2. Enhanced catalytic activity of Ag nanoparticles supported on polyacrylamide/polypyrrole/graphene oxide nanosheets for the reduction of 4-nitrophenol

    Science.gov (United States)

    Mao, Hui; Ji, Chunguang; Liu, Meihong; Cao, Zhenqian; Sun, Dayin; Xing, Zhiqiang; Chen, Xia; Zhang, Yu; Song, Xi-Ming

    2018-03-01

    High-density and well-dispersed Ag nanoparticles (Ag NPs) with a mean size of 20 nm have been successfully supported on the surface of polyacrylamide functionalized polypyrrole/graphene oxide (PAM/PPy/GO) nanosheets. The obtained Ag/PAM/PPy/GO composite nanosheets exhibited an excellent catalytic activity for reduction of 4-nitrophenol by NaBH4 with the kinetic reaction rate constant of 3.38 × 10-2 s-1 due to the synergistic effect of all the components of the composite nanosheets. The corresponding catalytic mechanism has been revealed by investigating the effect of different components of Ag/PAM/PPy/GO composite nanosheets on the catalytic performance: GO with the excellent two-dimensional structures offered large surface area for the immobilization of more Ag NPs; PPy with a high electric conductivity promoted the electron transport in the reduction of 4-NP; PAM did not only act as a good linker between Ag NPs and PPy/GO nanosheets for the synthesis of Ag/PAM/PPy/GO composite nanosheets, but also could facilitate the efficient contact between 4-NP and Ag NPs; Ag NPs were the catalytic active site for the reduction of 4-NP, respectively.

  3. A phosphate-dependent shift in redox state of cerium oxide nanoparticles and its effects on catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Sanjay; Dosani, Talib; Karakoti, Ajay S.; Kumar, Amit; Seal, Sudipta; Self, William

    2011-10-01

    Cerium oxide nanoparticles (CeNPs) have shown promise as catalytic antioxidants in cell culture and animal models as both superoxide dismutase and catalase mimetics. The reactivity of the cerium (Ce) atoms at the surface of its oxide particle is critical to such therapeutic properties, yet little is known about the potential for a protein or small molecule corona to form on these materials in vivo. Moreover Ce atoms in these active sites have the potential to interact with small molecule anions, peptides, or sugars when administered in culture or animal models. Several nanomaterials have been shown to alter or aggregate under these conditions, rendering them less useful for biomedical applications. In this work we have studied the change in catalytic properties of CeNPs when exposed to various biologically relevant conditions in vitro. We have found that CeNPs are resistant to broad changes in pH and also not altered by incubation in cell culture medium. However to our surprise phosphate anions significantly altered the characteristics of these nanomaterials and shifted the catalytic behavior due to the binding of phosphate anions to cerium. Given the abundance of phosphate in biological systems in an inorganic form, it is likely that the action of CeNPs as a catalyst may be strongly influenced by the local concentration of phosphate in the cells and/or tissues in which it has been introduced.

  4. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques

    International Nuclear Information System (INIS)

    Azabou, Samia; Najjar, Wahiba; Bouaziz, Mohamed; Ghorbel, Abdelhamid; Sayadi, Sami

    2010-01-01

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H 2 O 2 /ultraviolet radiations) at 25 deg. C and ((Al-Fe)PILC/H 2 O 2 ) at 50 deg. C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H 2 O 2 ), system operating at 50 deg. C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H 2 O 2 ) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  5. A compact process for the treatment of olive mill wastewater by combining wet hydrogen peroxide catalytic oxidation and biological techniques

    Energy Technology Data Exchange (ETDEWEB)

    Azabou, Samia [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Najjar, Wahiba [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Bouaziz, Mohamed [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia); Ghorbel, Abdelhamid [Laboratoire de Chimie des Materiaux et Catalyse, Faculte des Sciences de Tunis, Campus Universitaire, 2092 Tunis (Tunisia); Sayadi, Sami, E-mail: sami.sayadi@cbs.rnrt.tn [Laboratoire des BioProcedes, Centre de Biotechnologie de Sfax, BP 1177, 3018 Sfax (Tunisia)

    2010-11-15

    A system based on combined actions of catalytic wet oxidation and microbial technologies for the treatment of highly polluted OMW containing polyphenols was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process has been investigated in the semi-batch mode at atmospheric pressure, using aluminium-iron-pillared inter layer clay ((Al-Fe)PILC), under two different catalytic processes: ((Al-Fe)PILC/H{sub 2}O{sub 2}/ultraviolet radiations) at 25 deg. C and ((Al-Fe)PILC/H{sub 2}O{sub 2}) at 50 deg. C. The results show that raw OMW was resistant to the photocatalytic process. However ((Al-Fe)PILC/H{sub 2}O{sub 2}), system operating at 50 deg. C reduced considerably the COD, colour and total phenolic contents, and thus decreased the inhibition of the marine photobacteria Vibrio fischeri luminescence by 70%. This study also examined the feasibility of coupling WHPCO and anaerobic digestion treatment. Biomethanisation experiments performed with raw OMW or pre-treated OMW proved that pre-treatments with ((Al-Fe)PILC/H{sub 2}O{sub 2}) system, for more than 2 h, resulted in higher methane production. Both untreated OMW as well as 2-h pre-treated OMW revealed as toxic to anaerobic bacteria.

  6. Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

    Science.gov (United States)

    Chen, Fanglin; Wang, Yao

    2017-02-21

    Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

  7. Ce1-xFexO2 nanocatalysts for priority organic pollutants removal through catalytic wet air oxidation

    Directory of Open Access Journals (Sweden)

    Anushree

    2017-12-01

    Full Text Available A series of Ce1-xFexO2 nanocatalysts, prepared by co-precipitation method, were applied for the catalytic oxidation of priority organic pollutants present in paper industry wastewater. To investigate the synergic effect of various Fe contents, detailed characterizations of Ce1-xFexO2 were done by Raman, XPS, XRD, TEM and EDX techniques. The addition of Fe to CeO2 lattice increased the amount of oxygen vacancies, which have an efficient role in the oxidation of organic pollutants under oxygen-rich conditions. Ce0.4Fe0.6O2 catalyst showed the highest removal of TOC (72%, AOX (68%, chlorophenols (62% and chloroguaicols (86%. The superior catalytic activity of Ce0.4Fe0.6O2 is ascribed to its higher oxygen vacancy concentration. The presence of two oxidation states of Ce (4+,3+ and Fe (3+,2+ confirmed the role of redox couples in oxidation of organic pollutants.

  8. Performance of a Novel Hydrophobic Mesoporous Material for High Temperature Catalytic Oxidation of Naphthalene

    Directory of Open Access Journals (Sweden)

    Guotao Zhao

    2014-01-01

    Full Text Available A high surface area, hydrophobic mesoporous material, MFS, has been successfully synthesized by a hydrothermal synthesis method using a perfluorinated surfactant, SURFLON S-386, as the single template. N2 adsorption and TEM were employed to characterize the pore structure and morphology of MFS. Static water adsorption test indicates that the hydrophobicity of MFS is significantly higher than that of MCM-41. XPS and Py-GC/MS analysis confirmed the existence of perfluoroalkyl groups in MFS which led to its high hydrophobicity. MFS was used as a support for CuO in experiments of catalytic combustion of naphthalene, where it showed a significant advantage over MCM-41 and ZSM-5. SEM was helpful in understanding why CuO-MFS performed so well in the catalytic combustion of naphthalene. Experimental results indicated that MFS was a suitable support for catalytic combustion of large molecular organic compounds, especially for some high temperature catalytic reactions when water vapor was present.

  9. Catalytic oxidation of dibromomethane over Ti-modified Co3O4 catalysts: Structure, activity and mechanism.

    Science.gov (United States)

    Mei, Jian; Huang, Wenjun; Qu, Zan; Hu, Xiaofang; Yan, Naiqiang

    2017-11-01

    Ti-modified Co 3 O 4 catalysts with various Co/Ti ratios were synthesized using the co-precipitation method and were used in catalytic oxidation of dibromomethane (CH 2 Br 2 ), which was selected as the model molecule for brominated volatile organic compounds (BVOCs). Addition of Ti distorted the crystal structure and led to the formation of a Co-O-Ti solid solution. Co 4 Ti 1 (Co/Ti molar ratio was 4) achieved higher catalytic activity with a T 90 (the temperature needed for 90% conversion) of approximately 245°C for CH 2 Br 2 oxidation and higher selectivity to CO 2 at a low temperature than the other investigated catalysts. In addition, Co 4 Ti 1 was stable for at least 30h at 500ppm CH 2 Br 2 , 0 or 2vol% H 2 O, 0 or 500ppm p-xylene (PX), and 10% O 2 at a gas hourly space velocity of 60,000h -1 . The final products were CO x , Br 2 , and HBr, without the formation of other Br-containing organic byproducts. The high catalytic activity was attributed to the high Co 3+ /Co 2+ ratio and high surface acidity. Additionally, the synergistic effect of Co and Ti made it superior for CH 2 Br 2 oxidation. Furthermore, based on the analysis of products and in situ DRIFTs studies, a receivable reaction mechanism for CH 2 Br 2 oxidation over Ti-modified Co 3 O 4 catalysts was proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Preparation and characterization of Ni-Zr-O nanoparticles and its catalytic behavior for ethane oxidative dehydrogenation

    International Nuclear Information System (INIS)

    Wu Ying; Gao Jing; He Yiming; Wu Tinghua

    2012-01-01

    Ni-Zr-O nanoparticles with various Zr contents were prepared by a modified sol-gel method and characterized by X-ray diffraction (XRD), scanning/high-resolution transmission electron microscope (SEM/HRTEM), BET surface area analysis, H 2 temperature-programmed reduction (H 2 -TPR), X-ray photoelectron spectroscopy (XPS) and O 2 temperature-programmed desorption (O 2 -TPD). The oxidative dehydrogenation of ethane (ODHE) to ethylene was applied to evaluate catalytic performance of the samples. The results show that the doping of Zr affected the cell parameter and the chemical environment of the catalysts, indicating the existence of strong interaction between Ni and Zr. The interaction plays an important role in the lessened reducibility and the distribution of adsorbed oxygen species, consequently influence their catalytic performance. The best yield to ethylene was obtained over the 10% Ni-Zr-O catalyst with 60% ethane conversion and 66% ethylene selectivity.

  11. Production of gaseous fuel from jatropha oil by cerium oxide based catalytic fuel reactor and its utilisation on diesel engine

    Directory of Open Access Journals (Sweden)

    Mylswamy Thirunavukkarasu

    2016-01-01

    Full Text Available In this study, an attempt is made to produce a hydrocarbon fuel from jatropha vegetable oil for Diesel engine applications. The “catalytic cracking” a process recently introduced by the researchers is chosen as an alternative method to trans-esterification process to match the fuel properties to diesel. Jatropha vegetable oil was cracked into a gas using the cerium oxide catalyst in a fixed bed catalytic reactor. The produced gas is introduced at constant rate into the inlet manifold of the Diesel engine. The experimental work was carried out in single cylinder water cooled direct injection Diesel engine coupled with eddy current dynamometer. The combustion parameters are measured by AVL combustion analyser. From the experimental results, the increase in brake thermal efficiency of the engine for full load was observed to be 10% (relative compared with diesel. Notably, emissions such as HC, CO, and smoke are reduced by 18%, 61%, and 18%, respectively, when compared with diesel.

  12. Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Siefken, L.J.

    1999-01-01

    Models were designed to resolve deficiencies in the SCDAP/RELAP5/MOD3.2 calculations of the configuration and integrity of hot, partially oxidized cladding. These models are expected to improve the calculations of several important aspects of fuel rod behavior. First, an improved mapping was established from a compilation of PIE results from severe fuel damage tests of the configuration of melted metallic cladding that is retained by an oxide layer. The improved mapping accounts for the relocation of melted cladding in the circumferential direction. Then, rules based on PIE results were established for calculating the effect of cladding that has relocated from above on the oxidation and integrity of the lower intact cladding upon which it solidifies. Next, three different methods were identified for calculating the extent of dissolution of the oxidic part of the cladding due to its contact with the metallic part. The extent of dissolution effects the stress and thus the integrity of the oxidic part of the cladding. Then, an empirical equation was presented for calculating the stress in the oxidic part of the cladding and evaluating its integrity based on this calculated stress. This empirical equation replaces the current criterion for loss of integrity which is based on temperature and extent of oxidation. Finally, a new rule based on theoretical and experimental results was established for identifying the regions of a fuel rod with oxidation of both the inside and outside surfaces of the cladding. The implementation of these models is expected to eliminate the tendency of the SCDAP/RELAP5 code to overpredict the extent of oxidation of the upper part of fuel rods and to underpredict the extent of oxidation of the lower part of fuel rods and the part with a high concentration of relocated material. This report is a revision and reissue of the report entitled, Improvements in Modeling of Cladding Oxidation and Meltdown.

  13. Catalytic Performance of Zeolite-Supported Vanadia in the Aerobic Oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran

    DEFF Research Database (Denmark)

    Sádaba, Irantzu; Gorbanev, Yury; Kegnæs, Søren

    2013-01-01

    /Vis spectrophotometry. The H-beta zeolite catalysts were found to contain highly dispersed vanadium oxide species at all loadings, and provided the highest reaction selectivity towards DFF and the lowest metal leaching of the examined systems. In particular, 1 wt % V2O5/H-beta was found to be a stable, recyclable......The catalytic performance of zeolite-supported vanadia catalysts was examined for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) in organic solvents such as N,N-dimethylformamide (DMF), methyl isobutyl ketone, toluene, trifluorotoluene and DMSO. Catalysts based......, and non-leaching catalyst for the production of DFF under mild conditions in DMF as solvent, although with low DFF yield. To increase the yield, oxidation of HMF at elevated pressures was also investigated with this catalyst. Under optimized conditions, a reaction selectivity towards DFF of >99 % at 84...

  14. Selective catalytic reduction of nitric oxide with acetaldehyde over NaY zeolite catalyst in lean exhaust feed

    International Nuclear Information System (INIS)

    Schmieg, Steven J.; Cho, Byong K.; Oh, Se H.

    2004-01-01

    Steady-state selective catalytic reduction (SCR) of nitric oxide (NO) was investigated under simulated lean-burn conditions using acetaldehyde (CH 3 CHO) as the reductant. This work describes the influence of catalyst space velocity and the impact of nitric oxide, acetaldehyde, oxygen, sulfur dioxide, and water on NO x reduction activity over NaY zeolite catalyst. Results indicate that with sufficient catalyst volume 90% NO x conversion can be achieved at temperatures relevant to light-duty diesel exhaust (150-350C). Nitric oxide and acetaldehyde react to form N 2 , HCN, and CO 2 . Oxygen is necessary in the exhaust feed stream to oxidize NO to NO 2 over the catalyst prior to reduction, and water is required to prevent catalyst deactivation. Under conditions of excess acetaldehyde (C 1 :N>6:1) and low temperature ( x conversion is apparently very high; however, the NO x conversion steadily declines with time due to catalytic oxidation of some of the stored (adsorbed) NO to NO 2 , which can have a significant impact on steady-state NO x conversion. With 250ppm NO in the exhaust feed stream, maximum NO x conversion at 200C can be achieved with =400ppm of acetaldehyde, with higher acetaldehyde concentrations resulting in production of acetic acid and breakthrough of NO 2 causing lower NO x conversion levels. Less acetaldehyde is necessary at lower NO concentrations, while more acetaldehyde is required at higher temperatures. Sulfur in the exhaust feed stream as SO 2 can cause slow deactivation of the catalyst by poisoning the adsorption and subsequent reaction of nitric oxide and acetaldehyde, particularly at low temperature

  15. Adiabatic Gasification and Pyrolysis of Coffee Husk Using Air-Steam for Partial Oxidation

    OpenAIRE

    Catalina Rodriguez; Gerardo Gordillo

    2011-01-01

    Colombian coffee industry produces about 0.6 million tons of husk (CH) per year which could serve as feedstock for thermal gasification to produce gaseous and liquid fuels. The current paper deals with: (i) CH adiabatic gasification modeling using air-steam blends for partial oxidation and (ii) experimental thermogravimetric analysis to determine the CH activation energy (E). The Chemical Equilibrium with Applications Program (CEA), developed by NASA, was used to estimate the effect of equiva...

  16. Hydrogen Production via Synthetic Gas by Biomass/Oil Partial Oxidation

    Czech Academy of Sciences Publication Activity Database

    Hanika, Jiří; Lederer, J.; Tukač, V.; Veselý, Václav; Kováč, D.

    176-177, - (2011), s. 286-290 ISSN 1385-8947. [International Conference on Chemical Reactors CHEMREACTOR-19 /19./. Vienna, 05.09.2010-09.09.2010] R&D Projects: GA MPO 2A-2TP1/024 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrogen * biomass * partial oxidation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.461, year: 2011

  17. Polymer-Controlled Crystallization of Molybdenum Oxides from Peroxomolybdates: Structural Diversity and Application to Catalytic Epoxidation

    International Nuclear Information System (INIS)

    Munoz-Espf, R.; Burger, C.; Krishnan, C.; Chu, B.

    2008-01-01

    The influence of polyoxyethylene-containing polymers on the crystal structure and habit of molybdenum-oxide-based products crystallized from peroxomolybdate solutions was investigated. Polyoxyethylene homopolymers of various molar masses were compared with a polyoxyethylene alkyl ether and a triblock copolymer of polyoxyethylene and polypropylene. Conventional hydrothermal synthesis at temperatures between 70 and 180 C was compared with an ultrasonic pathway at 70 C. The structure of the products was investigated by small- and wide-angle X-ray scattering. Different crystal phases were obtained depending on the polymer concentration and the preparation methods. At 70 C, a compound with tentative formula MoO3-x(O2)x nH2O (n ? 1), showing X-ray diffraction patterns matching those of triclinic monohydrate molybdenum trioxide, was the product found in the absence of any polymer. However, small concentrations of any polyoxyethylene-containing polymer led to a monoclinic hemihydrate phase under the same conditions and temperature. At temperatures above 90 C, the patterns of the resulting products could be indexed according to orthorhombic anhydrous MoO3, although the blue color of certain samples indicated an oxygen deficiency. At high polymer concentrations and temperatures under 90 C, the material crystallized in an unusual primitive cubic structure, independent of the exact type of polyoxyethylene polymer used, with a very large cubic lattice constant of 5 nm. However, the molar mass and the structure of the polymer do influence the lattice constants of the final crystal leading to a slight decrease with increasing molar mass. At high polymer concentrations and 180 C, the product was identified as MoO2. The polymer acts not only as a structure-directing agent but also as a mild reducing agent, as judged from the nontrivial redox behavior of the molybdenum ions when the crystallization occurs in the presence of polymer. The excellent catalytic properties of

  18. Partial oxidation of n-hexadecane through decomposition of hydrogen peroxide in supercritical water

    KAUST Repository

    Alshammari, Y.M.

    2015-01-01

    © 2014 The Institution of Chemical Engineers. This work reports the experimental analysis of partial oxidation of n-hexadecane under supercritical water conditions. A novel reactor flow system was developed which allows for total decomposition of hydrogen peroxide in a separate reactor followed partial oxidation of n-hexadecane in a gasification reactor instead of having both reactions in one reactor. The kinetics of hydrothermal decomposition of hydrogen peroxide was studied in order to confirm its full conversion into water and oxygen under the desired partial oxidation conditions, and the kinetic data were found in a good agreement with previously reported literature. The gas yield and gasification efficiency were investigated under different operating parameters. Furthermore, the profile of C-C/C=C ratio was studied which showed the favourable conditions for maximising yields of n-alkanes via hydrogenation of their corresponding 1-alkenes. Enhanced hydrogenation of 1-alkenes was observed at higher O/C ratios and higher residence times, shown by the increase in the C-C/C=C ratio to more than unity, while increasing the temperature has shown much less effect on the C-C/C=C ratio at the current experimental conditions. In addition, GC-MS analysis of liquid samples revealed the formation of heavy oxygenated compounds which may suggest a new addition reaction to account for their formation under the current experimental conditions. Results show new promising routes for hydrogen production with in situ hydrogenation of heavy hydrocarbons in a supercritical water reactor.

  19. Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

    Science.gov (United States)

    Sun, Tonghua; Shen, Yafei; Jia, Jinping

    2014-02-18

    This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

  20. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  1. Effect of mesoporous g-C3N4 substrate on catalytic oxidation of CO over Co3O4

    Science.gov (United States)

    Yang, Heng; Lv, Kangle; Zhu, Junjiang; Li, Qin; Tang, Dingguo; Ho, Wingkei; Li, Mei; Carabineiro, Sónia A. C.

    2017-04-01

    Mesoporous graphitic carbon nitride (mpg-CN) was synthesized using Triton X-100, a surfactant containing a hydrophilic polyethylene oxide group and a tert-octyl-phenyl hydrophobic moiety, as a soft template. The obtained mpg-CN was used as a support for Co3O4, and this supported catalyst was used for CO oxidation. The effects of the amount of Triton X-100, weight ratio of Co3O4 to mpg-CN and calcination temperature on the catalytic performances for CO oxidation of Co3O4/mpg-CN composites were systematically studied. It was found that the presence of Triton X-100 not only retarded the polymerization of dicyandiamide, but also affected the microstructure of Co3O4. Bubbles formed because of the hydrophobic group of the surfactant Triton X-100 can be act as a soft template for the synthesis of mesoporous g-C3N4. The enhanced catalytic activity of Co3O4/mpg-CN was attributed to a synergistic effect, enlarged BET surface areas, increased Co3+ and lattice oxygen contents, and the porous structure of mpg-CN support. The high stability of 12.5% Co3O4/mpg-CN(1.0) makes it a promising catalyst for practical applications.

  2. Binuclear ruthenium(III) bis(thiosemicarbazone) complexes: synthesis, spectral, electrochemical studies and catalytic oxidation of alcohol.

    Science.gov (United States)

    Mohamed Subarkhan, M; Ramesh, R

    2015-03-05

    A new series of binuclear ruthenium(III) thiosemicarbazone complexes of general formula [(EPh3)2(X)2Ru-L-Ru(X)2(EPh3)2] (where E=P or As; X=Cl or Br; L=NS chelating bis(thiosemicarbazone ligands) has been synthesized and characterized by analytical and spectral (FT-IR, UV-Vis and EPR). IR spectra show that the thiosemicarbazones behave as monoanionic bidentate ligands coordinating through the azomethine nitrogen and thiolate sulphur. The electronic spectra of the complexes indicate that the presence of d-d and intense LMCT transitions in the visible region. The complexes are paramagnetic (low spin d(5)) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx≠gy≠gz) at 77K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (Ru(III)-Ru(III)/Ru(IV)-Ru(IV); Ru(III)-Ru(III)/Ru(II)-Ru(II)) within the potential range of 0.38-0.86V and -0.39 to -0.66 V respectively, versus Ag/AgCl. Further, the catalytic efficiency of one of the complexes [Ru2Cl2(AsPh3)4(L1)] (4) has been investigated in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide(NMO) as co-oxidant. The formation of high valent Ru(V)O species is proposed as catalytic intermediate for the catalytic cycle. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Oxidizer partial pressure window for YBa2Cu3O(7-x) thin film formation by metalorganic chemical vapor deposition

    Science.gov (United States)

    Chern, C. S.; Zhao, J.; Norris, P. E.; Garrison, S. M.; Yau, K.; Li, Y. Q.; Gallois, B. M.; Kear, B. H.

    1992-10-01

    We conducted a systematic study of oxidizer partial pressure effects on both the superconducting transport properties and structural properties of YBa2Cu3O(7-x) (YBCO) films grown by conventional metalorganic chemical vapor deposition (MOCVD). Superconducting YBCO thin films were grown in partial N2O pressures ranging from 0.4 to 45 Torr and at substrate temperatures of 500 and 700 C. We observed a window in oxidizer partial pressure within which YBCO thin films can be formed in the as-deposited state by the MOCVD process. A trend of increasing b-axis orientation as the oxidizer partial pressure increased was revealed by detailed X-ray diffraction. The reduction of superconducting properties for films grown at high oxidizer partial pressure might result from the lack of surface mobility.

  4. Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Nørskov, Jens Kehlet

    2010-01-01

    Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced...... and the effect of adsorbate-adsorbate interaction on the trends is discussed. We find that adsorbate-adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small...... influence on the position of the top of the volcano, that is, on which metal is the best catalyst....

  5. Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

    Science.gov (United States)

    Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

    2015-03-21

    Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Catalytic Properties of Fe-containing Layered Aluminosilicates in Photo-oxidation of Dye “Methyl Green”

    Science.gov (United States)

    Shadrina, O. A.; Dashinamzhilova, E. Ts; Khankhasaeva, S. Ts

    2017-11-01

    The iron-containing materials with an iron content of 40 mg/g and 52.5 mg/g, a specific surface area of 107 m2/g and 96 m2/g are developed on the basis of natural layered aluminosilicate (montmorillonite) and polyhydroxo complexes of iron. It is shown that the materials exhibit high catalytic activity in the photo-oxidation of dye “Methyl Green”. The influence of physicochemical parameters (loading of the catalyst, a ratio of initial concentrations [H2O2]/[MG] on the efficiency of the dye photo-oxidation was established. The optimum conditions, which made it possible to achieve high mineralization and 100 % the dye oxidation efficiency were determined: the catalyst loading equal to 1.0 g/l and the ratio of [H2O2] and [MG] equal to stoichiometric ratio (55 mol/mol). The decrease of the total organic carbon content after photo-oxidation reaction was 56.5%. The average value of the quantum yield of the dye photo-oxidation was to 0.30 mol/Einstein. The results of the conducted research show that the developed iron-containing materials are the promising catalysts for photo-Fenton processes of oxidative degradation of organic compounds. The materials are of interest for use in wastewater treatment processes from toxic organic pollutants.

  7. Denitration of medium level liquid radioactive wastes by catalytic destruction of nitrogen oxides

    International Nuclear Information System (INIS)

    Donato, A.; Ricci, G.

    1984-01-01

    The catalytic abatement by means of NH 3 of the NOsub(x) produced in the radwaste conditioning has been studied. With reference to the gas produced in a bituminization plant, the thermodynamics and the chemistry of the NOsub(x) catalytic reduction to nitrogen and H 2 O have been evaluated. The following operational parameters have been experimentally studied: the catalyst bed temperature; the gas residence time; the vapour concentration; the NOsub(x) concentration; the gas velocity; the catalyst grain size distribution; the catalyst time-life. Abatement yields of the order of 99,5% have been obtained following experimental conditions must be selected. In the case of a bituminization plant, a NOsub(x) catalytic reactor, if installed between the evaporator denitrator and the condenser, could reduce to less than 1/100 the volume of the NaNO 3 secondary wastes produced by the gas scrubbing

  8. Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

    International Nuclear Information System (INIS)

    Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

    2015-01-01

    Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY H2 , TRE and CR could exhibit up to 14.32 mmol·gTOC −1 , 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H 2 yield (GY H2 ), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY H2 , CR and TRE were established with Box–Behnken design. GY H2 , CR and TRE reached up to 14.32 mmol·gTOC −1 , 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO 2 and H 2 were the most abundant gaseous products. As a product of nitrogen-containing organics, NH 3 has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient

  9. Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

    Science.gov (United States)

    Mahmoodlu, Mojtaba G.; Hassanizadeh, S. Majid; Hartog, Niels; Raoof, Amir

    2014-08-01

    The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw = 0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

  10. Preparation of magnetic imprinted graphene oxide composite for catalytic degradation of Congo red under dark ambient conditions.

    Science.gov (United States)

    Yang, Xiaochao; You, Xiaoxiao; Zhang, Bin; Guo, Chuigen; Yu, Chaosheng

    2017-10-01

    Magnetic imprinted N-doped P25/Fe 3 O 4 -graphene oxide (MIGNT) was prepared with methyl orange as the dummy template and pyrrole as functional monomer for catalytic degradation of Congo red (CR). Hummers method and the hydrothermal method were used to synthesize Fe 3 O 4 -GO and N-doped P25, respectively. The results of adsorption and degradation experiments showed that the adsorption capacity and catalytic degradation ability of the imprinted composite for CR were obviously higher than those of a non-imprinted one. Moreover, the effect factors on degradation efficiency of CR, such as the initial concentration of CR, catalysis time, pH of the solution and temperature, were investigated. The MIGNT was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, a physical property measurement system and a thermal gravimetric analyzer. The degradation products of CR were detected with high performance liquid chromatography and a mass spectrometer. The MIGNT was a brand-new imprinted composite and had high degradation efficiency for CR under dark ambient conditions. The MIGNT could be recycled conveniently, due to its magnetic property, and could be used as an effective, environmentally friendly and low-cost catalytic degradation material for the treatment of water contaminated by CR.

  11. Improved surface-enhanced Raman and catalytic activities of reduced graphene oxide-osmium hybrid nano thin films

    Science.gov (United States)

    Kavitha, C.; Bramhaiah, K.; John, Neena S.; Aggarwal, Shantanu

    2017-09-01

    Reduced graphene oxide-osmium (rGO-Os) hybrid nano dendtrites have been prepared by simple liquid/liquid interface method for the first time. The method involves the introduction of phase-transfered metal organic precursor in toluene phase and GO dispersion in the aqueous phase along with hydrazine hydrate as the reducing agent. Dendritic networks of Os nanoparticles and their aggregates decorating rGO layers are obtained. The substrate shows improved catalytic and surface-enhanced activities comparable with previous reports. The catalytic activity was tested for the reduction of p-nitroaniline into p-phenyldiamine with an excess amount of NaBH4. The catalytic activity factors of these hybrid films are 2.3 s-1 g-1 (Os film) and 4.4 s-1 g-1 (rGO-Os hybrid film), which are comparable with other noble metal nanoparticles such as Au, Ag, but lower than Pd-based catalysts. Surface-enhanced Raman spectroscopy (SERS) measurements have been done on rhodamine 6G (R6G) and methylene blue dyes. The enhancement factor for the R6G adsorbed on rGO-Os thin film is 1.0 × 105 and for Os thin film is 7 × 103. There is a 14-fold enhancement observed for Os hybrids with rGO. The enhanced catalytic and SERS activities of rGO-Os hybrid thin film prepared by simple liquid/liquid interface method open up new challenges in electrocatalytic application and SERS-based detection of biomolecules.

  12. Removal of Humic Substances from Water by Advanced Oxidation Process Using UV/TiO2 Photo Catalytic Technology

    Directory of Open Access Journals (Sweden)

    Hassan Khorsandi

    2009-01-01

    Full Text Available Humic substances have been known as precursors to disinfection by-products. Because conventional treatment processes cannot meet disinfection by-product standards, novel methods have been increasingly applied for the removal of disinfection by-products precursors. The UV/TiO2 process is one of the advanced oxidation processes using the photocatalytic technology. The most important advantages of this process are its stability and high efficiency removal. The present study aims to investigate the effect of UV/TiO2 photo-catalytic technology on removal of humic substances. The study was conducted in a lab-scale batch photo-catalytic reactor using the interval experimental method. The UV irradiation source was a low pressure mercury vapor lamp 55w that was axially centered and was immersed in a humic acids solution within a stainless steel tubular 2.8 L reaction volume. Each of the samples taken from the UV/TiO2 process and other processes studied were analyzed for their dissolved organic carbon, UV absorbance at 254nm, and specific UV254 absorbance. The results indicated the high efficiency of the UV/TiO2 photo-catalytic process (TiO2=0.1 g/L and pH=5, compared to other processes, for humic substances removal from water sources. The process was also found to be capable of decreasing the initial dissolved organic carbon from 5 to 0.394 mg/L. The Specific UV254 Absorbance of 2.79 L/mg.m was attained after 1.5 hr. under photo-catalytic first order reaction (k= 0.0267 min-1. It may be concluded that the UV/TiO2 process can provide desirable drinking water quality in terms of humic substance content.

  13. Experimental study of methane partial oxidation on Ni-YSZ anode of solid oxide fuel cells

    Science.gov (United States)

    Iwai, Hiroshi; Tada, Koshi; Kishimoto, Masashi; Saito, Motohiro; Yoshida, Hideo

    2017-08-01

    The effects of oxygen addition to methane directly supplied to solid oxide fuel cells were investigated. Fundamental experiments were conducted using Ni-YSZ (yttria-stabilized zirconia) cermet as a typical anode material, and Ni-YSZ catalysts having different streamwise lengths were fabricated on YSZ flat plates. A premixed gas of methane, oxygen, nitrogen and steam was supplied to a test catalyst set in a rectangular test channel. The exhaust gas compositions and the surface temperature distributions of the test catalysts were measured. It was found that the oxidation of methane prominently proceeded near the upstream edge of the catalyst followed by steam/dry reforming reactions downstream. This resulted in the formation of a high-temperature region, leading to a large temperature gradient in the streamwise direction.

  14. Partial Oxidation of n-Butane over a Sol-Gel Prepared Vanadium Phosphorous Oxide

    Directory of Open Access Journals (Sweden)

    Juan M. Salazar

    2013-01-01

    Full Text Available Vanadium phosphorous oxide (VPO is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO4∙0.5H2O (the precursor followed by in situ activation to produce (VO2P2O7 (the active phase. This paper discusses an alternative synthesis method based on sol-gel techniques. Vanadium (V triisopropoxide oxide was reacted with ortho-phosphoric acid in an aprotic solvent. The products were dried at high pressure in an autoclave with a controlled excess of solvent. This procedure produced a gel of VOPO4 with interlayer entrapped molecules. The surface area of the obtained materials was between 50 and 120 m2/g. Alcohol produced by the alkoxide hydrolysis reduced the vanadium during the drying step, thus VOPO4 was converted to the precursor. This procedure yielded non-agglomerated platelets, which were dehydrated and evaluated in a butane-air mixture. Catalysts were significantly more selective than the traditionally prepared materials with similar intrinsic activity. It is suggested that the small crystallite size obtained increased their selectivity towards maleic anhydride.

  15. Catalytic wet-air oxidation of lignin in a three-phase reactor with aromatic aldehyde production

    Directory of Open Access Journals (Sweden)

    Sales F.G.

    2004-01-01

    Full Text Available In the present work a process of catalytic wet air oxidation of lignin obtained from sugar-cane bagasse is developed with the objective of producing vanillin, syringaldehyde and p-hydroxybenzaldehyde in a continuous regime. Palladium supported on g-alumina was used as the catalyst. The reactions in the lignin degradation and aldehyde production were described by a kinetic model as a system of complex parallel and series reactions, in which pseudo-first-order steps are found. For the purpose of producing aromatic aldehydes in continuous regime, a three-phase fluidized reactor was built, and it was operated using atmospheric air as the oxidizer. The best yield in aromatic aldehydes was of 12%. The experimental results were compatible with those values obtained by the pseudo-heterogeneous axial dispersion model (PHADM applied to the liquid phase.

  16. Synthesis of Ru nanoparticles confined in magnesium oxide-modified mesoporous alumina and their enhanced catalytic performance during ammonia decomposition

    KAUST Repository

    Tan, Hua

    2012-09-01

    In this work, Ru nanoparticles confined in the channels of ordered mesoporous alumina (MA) and magnesium oxide-modified ordered MA are prepared for the first time via a two-solvent technique, combined with the amorphous citrate route. Structural characterizations reveal that uniform 2-3 nm Ru nanoparticles are highly dispersed in the blockage-free channels of mesoporous supports. The Ru nanoparticles confined in MA modified with 20% molar ratio magnesium oxide exhibited a high catalytic activity and stability during ammonia decomposition due to the optimized particle size, basic support, lack of chlorine, and confined space provided by the channels of the mesoporous supports. © 2012 Elsevier B.V. All rights reserved.

  17. System and method for controlling ammonia levels in a selective catalytic reduction catalyst using a nitrogen oxide sensor

    Science.gov (United States)

    None

    2017-07-25

    A system according to the principles of the present disclosure includes an air/fuel ratio determination module and an emission level determination module. The air/fuel ratio determination module determines an air/fuel ratio based on input from an air/fuel ratio sensor positioned downstream from a three-way catalyst that is positioned upstream from a selective catalytic reduction (SCR) catalyst. The emission level determination module selects one of a predetermined value and an input based on the air/fuel ratio. The input is received from a nitrogen oxide sensor positioned downstream from the three-way catalyst. The emission level determination module determines an ammonia level based on the one of the predetermined value and the input received from the nitrogen oxide sensor.

  18. Novel Cage-Like Hexanuclear Nickel(II Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

    Directory of Open Access Journals (Sweden)

    Alexey N. Bilyachenko

    2016-05-01

    Full Text Available New hexanuclear nickel(II silsesquioxane [(PhSiO1.512(NiO6(NaCl] (1 was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,512(NiO6(NaCl(C4H8O213(PhCN2(H2O2 and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

  19. Comparison of catalytic activity of Ru(3) cloride and Ru(8) oxide in oxidation of 2-methyl cyclohexanol by Ce(4) sulfate in aqueous solutions of sulfuric acid

    International Nuclear Information System (INIS)

    Tondeon, P.K.; Krishna, B.

    1985-01-01

    The catalytic activity of Ru(3) chloride and Ru(8) oxide in the course of 2-methyl cyclohexanol (MCH) oxidation by Ce(4) sulfate in sulfuric acid is compared. In the presepce of RU(3) the reaction kinetics obeys the equation of the first order relative to organic substrate concentration (at its low concentrations) and tends to zero order at its higher concentrations. For ruthenium (3) chloride the first order is observed. In the presence of Ru(8) the reaction rate is proportional to substrate and catalyst concentrations only in the low concentrations region of the latter while at RU(8) high concentrations a decrease of the catalytic effect is observed. In both cases the process rate is inversely proportional to the sulfuric acid concentration square at its great values and directly proportional-at small ones. An assumption is made that cyclic alcohol oxidation occurs through the activated complex formed as a result of alcohol interaction with Ru(3) or ruthenium (8) hydride

  20. Benzenoid-like CuFeO2@reduced graphene oxide: Facile synthesis and its excellent catalytic performance in selective oxidation

    Science.gov (United States)

    Xu, Tingting; He, Guangyu; Zhao, Yitao; Gu, Hanyun; Jiang, Zhengyuan; Chen, Qun; Sun, Xiaoqiang; Chen, Haiqun

    2016-12-01

    A novel flake composite benzenoid-like CuFeO2@reduced graphene oxide (CuFeO2@RGO) was fabricated via a one-step low temperature solvothermal route. The obtained samples were characterized by XRD, FTIR, Raman, SEM, TEM and XPS, which indicated that the hexagonal CuFeO2 nanocrystals sized 150-200 nm were well dispersed on the surface of the RGO sheets. For the first time, we applied such CuFeO2@RGO composite as a Fenton-like catalyst in selective oxidation of phenol to dihydroxybenzenes with H2O2 as oxidant. The results showed that the CuFeO2@RGO composite exhibited remarkably enhanced catalytic ability compared with the previously reported CuFe2O4-RGO system. The introduction of RGO in the composite was propitious to increase the specific surface area and promoted the dispersibility of CuFeO2 nanocrystals, as well as the formation of unique hexagonal CuFeO2 with Cu (I) and Fe (III) as the active sites, which synergistically accounted for the enhancement of catalytic activity. Moreover, the stability of the catalyst was investigated.

  1. Microwave-Assisted Synthesis of Nickel Oxide Nanoparticles Using Coriandrum sativum Leaf Extract and Their Structural-Magnetic Catalytic Properties

    Directory of Open Access Journals (Sweden)

    Ramakrishnan Azhagu Raj

    2017-04-01

    Full Text Available In this paper, using Coriandrum sativum L., a leaf-extracted, assisted microwave method (MM was used to synthesize nickel oxide formation. We synthesized nickel oxide nanoparticles (NiO with a crystal size in the range of 15–16 nm by a Coriandrum sativum leaf-assisted microwave method (LAMM. The synthesized materials show that an X-ray diffraction (XRD study confirmed the formation of a single phase structure exhibiting a crystallite size in the range of 15–16 nm using Scherrer’s method. The nickel oxide prepared by the MM had a surface area of 60.35 m2/g, pore volume of 0.9427 cm3/g and an average pore diameter of 13.27 Å. Surface morphology was analyzed by the scanning electron microscope (SEM, X-ray photoelectron spectroscope, Brunauer-Emmett-Teller (BET analysis, and the vibrating sample magnetometer (VSM. Catalytic activity (CA tended toward the oxidation of styrene to benzaldehyde. The inexpensive catalyst tested is likely effective as a catalyst due to synergistic interactions between metal oxides with high dispersion. In comparison with other findings, LAMM is easy and eco-friendly. The current study obtained nanocrystalline NiO that was suitable for potential applications in catalysis. The synthesized NiO could potentially be used in therapeutic field due to their competent antibacterial activity.

  2. Catalytic Performance of Co3O4 on Different Activated Carbon Supports in the Benzyl Alcohol Oxidation

    Directory of Open Access Journals (Sweden)

    Misael Cordoba

    2017-12-01

    Full Text Available Co3O4 particles were supported on a series of activated carbons (G60, CNR, RX3, and RB3. Incipient wetness method was used to prepare these catalysts. The effect of the structural and surface properties of the carbonaceous supports during oxidation of benzyl alcohol was evaluated. The synthetized catalysts were characterized via IR, TEM, TGA/MS, XRD, TPR, AAS, XPS, and N2 adsorption/desorption isotherm techniques. Co3O4/G60 and Co3O4/RX3 catalysts have high activity and selectivity on the oxidation reaction reaching conversions above 90% after 6 h, without the presence of promoters. Catalytic performances show that differences in chemistry of support surface play an important role in activity and suggest that the presence of different ratios of species of cobalt and oxygenated groups on surface in Co3O4/G60 and Co3O4/RX3 catalysts, offered a larger effect synergic between both active phase and support increasing their catalytic activity when compared to the other tested catalysts.

  3. Catalytic Hydrolysis of Ammonia Borane by Cobalt Nickel Nanoparticles Supported on Reduced Graphene Oxide for Hydrogen Generation

    Directory of Open Access Journals (Sweden)

    Yuwen Yang

    2014-01-01

    Full Text Available Well dispersed magnetically recyclable bimetallic CoNi nanoparticles (NPs supported on the reduced graphene oxide (RGO were synthesized by one-step in situ coreduction of aqueous solution of cobalt(II chloride, nickel (II chloride, and graphite oxide (GO with ammonia borane (AB as the reducing agent under ambient condition. The CoNi/RGO NPs exhibits excellent catalytic activity with a total turnover frequency (TOF value of 19.54 mol H2 mol catalyst−1 min−1 and a low activation energy value of 39.89 kJ mol−1 at room temperature. Additionally, the RGO supported CoNi NPs exhibit much higher catalytic activity than the monometallic and RGO-free CoNi counterparts. Moreover, the as-prepared catalysts exert satisfying durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB, which make the practical reusing application of the catalysts more convenient. The usage of the low-cost, easy-getting catalyst to realize the production of hydrogen under mild condition gives more confidence for the application of ammonia borane as a hydrogen storage material. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to facile preparation of other RGO-based metallic systems.

  4. The surface behaviour and catalytic properties of Nd2-XSrXCoO4±Λ mixed oxides

    Directory of Open Access Journals (Sweden)

    Laitao Luo

    2006-12-01

    Full Text Available The mixed oxides, Nd2-xSrxCoO4±λ (0.4 ≤ x ≤ 1.2, ( = non-stochiometric oxygen with the K2NiF4 structure were prepared by the polyglycol gel method and used as catalysts for NO reduction. The samples were investigated by IR, TPD, TPR, and XRD methods and iodometry and the effects of the coefficient x on the structure and catalytic activity of the samples were studied. The results show that the Nd2-xSrxCoO4±λ mixed oxides have the K2NiF4 structure; other phases are found when x 1.2. The amount of Co3+ and the lattice oxygen in Nd2-xSrxCoO4±λ increase with increasing x. The catalytic activity of Nd2-xSrxCoO4±λfor NO reduction is closely correlated with the concentration of oxygen vacancies and the amount of Co3+.

  5. Anchoring Tri(8-QuinolinolatoIron Onto Sba-15 for Partial Oxidation of Benzyl Alcohol Using Water as the Solvent

    Directory of Open Access Journals (Sweden)

    Yang Xiaoyuan

    2014-09-01

    Full Text Available Tri(8-quinolinolatoiron complex immobilized onto SBA-15 catalyst has been synthesized through a stepwise procedure. The characterization results indicated that the BET surface area, total pore volume and average pore width decrease after stepwise modification of SBA-15, while the structure keeps intact. Catalytic tests showed that FeQ3-SBA-15 catalyzes the oxidation reaction well with 34.8% conversion of benzyl alcohol and 74.7% selectivity to benzaldehyde when water is used as the solvent after 1 h reaction. In addition, homogeneous catalyst tri(8-quinolinolatoiron exhibits very bad catalytic behavior using water as the solvent.

  6. Catalytic Oxidation of CW Agents Using H2O2 in Ionic Liquids

    National Research Council Canada - National Science Library

    Nelson, William M

    2003-01-01

    Partial contents: Structures of ionic, Common Cationic Surfactants, Micelles to Micelles to Microemulsions, Microemulsion Formulations,Structures of HD, Structures of HD, VX, VX, GB, and GD, Decontamination...

  7. Supported manganese oxide on TiO{sub 2} for total oxidation of toluene and polycyclic aromatic hydrocarbons (PAHs): Characterization and catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Aboukaïs, Antoine, E-mail: aboukais@univ-littoral.fr [Univ Lille Nord de France, 59000 Lille (France); Equipe Catalyse, UCEIV, EA 4492, MREI, ULCO, 59140 Dunkerque (France); Abi-Aad, Edmond [Univ Lille Nord de France, 59000 Lille (France); Equipe Catalyse, UCEIV, EA 4492, MREI, ULCO, 59140 Dunkerque (France); Taouk, Bechara [Laboratoire de Sécurité des procédés Chimiques (LSPC), EA 4704, INSA Rouen, Avenue de l' Université, 76801 Saint Etienne du Rouvray (France)

    2013-11-01

    Manganese oxide catalysts supported on titania (TiO{sub 2}) were prepared by incipient wetness impregnation method in order to elaborate catalysts for total oxidation of toluene and PAHs. These catalysts have been characterized by means of X-ray diffraction (XRD), electron paramagnetic resonance (EPR), temperature programmed reduction (TPR) and temperature programmed desorption (TPD). It has been shown that for the 5%Mn/TiO{sub 2} catalyst the reducibility and the mobility of oxygen are higher compared, in one side, to other x%Mn/TiO{sub 2} samples and, in another side, to catalysts where TiO{sub 2} support was replaced by γ-Al{sub 2}O{sub 3} or SiO{sub 2}. It has been shown that the content of manganese loading on TiO{sub 2} has an effect on the catalytic activity in the toluene oxidation. A maximum of activity was obtained for the 5%Mn/TiO{sub 2} catalyst where the total conversion of toluene was reached at 340 °C. This activity seems to be correlated to the presence of the Mn{sup 3+}/Mn{sup 4+} redox couple in the catalyst. When the Mn content increases, large particles of Mn{sub 2}O{sub 3} appear leading then to the decrease in the corresponding activity. In addition, compared to both other supports, TiO{sub 2} seems to be the best to give the best catalytic activity for the oxidation of toluene when it is loaded with 5% of manganese. For this reason, the latter catalyst was tested for the abatement of some PAHs. The light off temperature of PAHs compounds increases with increasing of benzene rings number and with decreasing of H/C ratio. All of PAHs are almost completely oxidized and converted at temperatures lower than 500 °C. - Highlights: • Preparation of x%MnO{sub 2}/TiO{sub 2} catalysts. • Catalytic oxidation tests of toluene and PAHs. • EPR, TPR and TPD characterizations of Mn(II) and Mn(IV) ions.

  8. Catalytic Oxidation of Phenol over Zeolite Based Cu/Y-5 Catalyst: Part 1: Catalyst Preparation and Characterization

    Directory of Open Access Journals (Sweden)

    K. Maduna Valkaj

    2015-01-01

    Full Text Available The necessity to remove organic pollutants from the industrial wastewater streams has forced the development of new technologies that can produce better results in terms of pollutant removal and process efficiency in combination with low investment and operating costs. One of the new emerging processes with a potential to fulfil these demands is catalytic wet peroxide oxidation, commonly known as the CWPO process. The oxidative effect of the hydrogen peroxide is intensified by the addition of a heterogeneous catalyst that can reduce the operating conditions to atmospheric pressure and temperatures below 383 K. Zeolites, among others, are especially appealing as catalysts for selective oxidation processes due to their unique characteristics such as shape selectivity, thermal and chemical stability, and benign effect on nature and the living world. In this work, catalytic activity, selectivity and stability of Cu/Y-5 zeolite in phenol oxidation with hydrogen peroxide was examined. Catalyst samples were prepared by ion exchange method of the protonic form of commercial zeolite. The catalysts were characterized with powder X-ray diffraction (XRD, scanning electron microscopy (SEM, and AAS elemental analysis, while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and in the temperature range from 323 to 353 K. The catalyst was prepared in powdered form and the mass fraction of the active metal component on the zeolite was 3.46 %. The initial concentration of phenol solution was equal to 0.01 mol dm−3 and the concentration of hydrogen peroxide ranged from 0.01 to 0.10 mol dm−3. The obtained experimental data was tested to a proposed kinetic model for phenol oxidation r = k1 cF cVP and hydrogen peroxide decomposition rHP = k2 cHP. The kinetic parameters were estimated using the Nelder

  9. Effect of the preparation method on the structural and catalytic properties of spinel cobalt-iron oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hammiche-Bellal, Yasmina, E-mail: yasminahammiche@gmail.com [Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Djadoun, Amar [Laboratoire de Géophysique, FSTGAT, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Meddour-Boukhobza, Laaldja; Benadda, Amel [Laboratoire des Matériaux Catalytiques et Catalyse en Chimie Organique, Faculté de Chimie, USTHB, BP32 El Alia, Bab Ezzouar, 16111, Alger (Algeria); Auroux, Aline [Université Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de Recherches sur la Catalyse et l' Environnement de Lyon, 2 Avenue Albert Einstein, F-69626, Villeurbanne (France); Berger, Marie-Hélène [Centre des Matériaux PIERRE-MARIE Fourt, UMR 7633, Paris (France); Mernache, Fateh [UDEC-CRND, COMENA, BP 43 Draria, 16050, Alger (Algeria)

    2016-07-01

    Spinel cobalt-iron oxide was synthesized by co-precipitation and hydrothermal routes. The effect of the co-precipitation experimental conditions, the calcination temperature and the hydrothermal synthesis time and temperature on the properties of the solids was studied. The prepared powders were evaluated as catalysts in the ethanol combustion reaction, and were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM/EDX), nitrogen adsorption–desorption isotherms (BET, BJH) and temperature programmed reduction (TPR) techniques. Using chloride salts as starting materials and sodium hydroxide as precipitating agent, the CoFe{sub 2}O{sub 4} prepared powders displayed a mesoporous structure with a pore distribution strongly dependent on the experimental conditions. A monophasic spinel phase in the case of the calcined solids was obtained while the hydrothermal process led to the formation of a mixture of single oxides in addition to the spinel phase. The variation of the crystallite size and the lattice parameter as a function of calcination temperature was similar, whereas this variation found to be irregular when the synthesis residence time in autoclave was increased. The hydrothermally treated solids show the best catalytic performance in the total oxidation of ethanol. The catalytic behavior was correlated with the crystallite size and the reduction temperature of cobalt species determined by the TPR analysis. - Highlights: • Pure CoFe{sub 2}O{sub 4} phase is obtained by co-precipitation method at calcination temperatures 500–900 °C. • The temperature of co-precipitation procedure influences strongly the growth of the solids during the calcination step. • The hydrothermal synthesis gives a mixture of oxides; CoFe{sub 2}O{sub 4} is the predominant phase. • The CoFe{sub 2}O{sub 4} spinel showed a good catalytic reactivity in the ethanol combustion reaction. • The catalysts prepared by hydrothermal process are more reactive and

  10. Selective catalytic reduction of nitric oxide by ammonia over Cu-exchanged Cuban natural zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Moreno-Tost, Ramon; Santamaria-Gonzalez, Jose; Rodriguez-Castellon, Enrique; Jimenez-Lopez, Antonio [Departamento de Quimica Inorganica, Cristalografia y Mineralogia, Facultad de Ciencias, Unidad Asociada del Instituto de Catalisis y Petroleoquimica, CSIC, Universidad de Malaga, Campus de Teatinos, 29071 Malaga (Spain); Autie, Miguel A.; Glacial, Marisol Carreras [Centro Nacional de Investigaciones Cientificas, Ciudad de la Habana, La Habana (Cuba); Gonzalez, Edel [Instituto Superior Pedagogico ' Enrique Jose Varona' , La Habana (Cuba); Pozas, Carlos De las [Centro de Gerencia de Programas y Proyectos Priorizados, La Habana (Cuba)

    2004-07-15

    The catalytic selective reduction of NO over Cu-exchanged natural zeolites (mordenite (MP) and clinoptilolite (HC)) from Cuba using NH{sub 3} as reducing agent and in the presence of excess oxygen was studied. Cu(II)-exchanged zeolites are very active catalysts, with conversions of NO of 95%, a high selectivity to N{sub 2} at low temperatures, and exhibiting good water tolerance. The chemical state of the Cu(II) in exchanged zeolites was characterized by H{sub 2}-TPR and XPS. Cu(II)-exchanged clinoptilolite underwent a severe deactivation in the presence of SO{sub 2}. However, Cu(II)-exchanged mordenite not only maintained its catalytic activity, but even showed a slight improvement after 20h of reaction in the presence of 100ppm of SO{sub 2}.

  11. Selective catalytic reduction of nitric oxide by ammonia over Cu-exchanged Cuban natural zeolites

    International Nuclear Information System (INIS)

    Moreno-Tost, Ramon; Santamaria-Gonzalez, Jose; Rodriguez-Castellon, Enrique; Jimenez-Lopez, Antonio; Autie, Miguel A.; Glacial, Marisol Carreras; Gonzalez, Edel; Pozas, Carlos De las

    2004-01-01

    The catalytic selective reduction of NO over Cu-exchanged natural zeolites (mordenite (MP) and clinoptilolite (HC)) from Cuba using NH 3 as reducing agent and in the presence of excess oxygen was studied. Cu(II)-exchanged zeolites are very active catalysts, with conversions of NO of 95%, a high selectivity to N 2 at low temperatures, and exhibiting good water tolerance. The chemical state of the Cu(II) in exchanged zeolites was characterized by H 2 -TPR and XPS. Cu(II)-exchanged clinoptilolite underwent a severe deactivation in the presence of SO 2 . However, Cu(II)-exchanged mordenite not only maintained its catalytic activity, but even showed a slight improvement after 20h of reaction in the presence of 100ppm of SO 2

  12. The influence of partial oxidation mechanisms on tar destruction in TwoStage biomass gasification

    DEFF Research Database (Denmark)

    Ahrenfeldt, Jesper; Egsgaard, Helge; Stelte, Wolfgang

    2013-01-01

    and conversion. The study identifies the following major impact factors regarding tar content in the producer gas: oxidation temperature, excess air ratio and biomass moisture content. In a experimental setup, wood pellets were pyrolyzed and the resulting pyrolysis gas was transferred in a heated partial...... tar destruction and a high moisture content of the biomass enhances the decomposition of phenol and inhibits the formation of naphthalene. This enhances tar conversion and gasification in the char-bed, and thus contributes in-directly to the tar destruction....

  13. Hydrogen or Soot ?: Partial Oxidation of High-Boiling Hydrocarbon Wastes

    OpenAIRE

    Lederer, J.

    2014-01-01

    This paper is focussed to research of the influence of process parameters of partial oxidation like quality of hydrocarbon raw materials, which differed in their stock properties (especially the boiling point and viscosity), on the composition of output gas (selectivity of the process) and also on the formation extent of soot which can be used as an excellent and valued sorbent CHEZACARB(™) and/or filler in rubber industry, e.g. for automotive tires. The effects of steam flow rate and oxygen...

  14. Zeolite encapsulated Fe-porphyrin for catalytic oxidation with iodobenzene diacetate (PhI(OAc){sub 2})

    Energy Technology Data Exchange (ETDEWEB)

    Karimipour, G.; Rezaei, M.; Ashouri, D. [Yasouj University, Department of Chemistry, 75918-74831 Yasouj (Iran, Islamic Republic of)

    2013-07-01

    meso-Tetrakis(3-pyridyl)porphyrin ato iron(III) chloride encapsulated on NaY Zeolite [Fe(T-3-PyP)-NaY] was synthesized as a heterogeneous ship-in-a-bottle type catalyst and characterized by Fourier transform infrared, atomic absorption, diffused reflectance UV-Vis, X-ray diffraction and scanning electron microscopy analysis. The catalytic activity of Fe(T-3-PyP-NaY was examined for the epoxidation of cyclohexene by PhI(OAc){sub 2} in CH{sub 3}CN/H{sub 2}O (5:1) and compared to that of Fe(T-3-PyP) as a homogeneous catalyst. We found that the heterogeneous catalyst Fe(T-3-PyP-NaY was stable and reusable for several times, and provided a mild condition and exhibited high activity and selectivity in the oxidation of alkenes to epoxides (16-94%). As representative examples for the use of Fe(T-3-PyP-NaY/ PhI(OAc){sub 2} in organic oxidations, oxidation of 4-nitro benzylalcohol to 4-nitrobenzaldehyde (97%), oxidative dehydrogenation of diethyl 4-(2,6-dichlorophenyl)-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate to the corresponding pyridine (100%), diphenylacetic acid to benzophenone (64%) was achieved. (Author)

  15. An investigation of alumina-supported catalysts for the selective catalytic oxidation of ammonia in biomass gasification

    Energy Technology Data Exchange (ETDEWEB)

    Darvell, L.I.; Jones, J.M.; Ross, A.B.; Williams, A. [Department of Fuel and Energy, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); Heiskanen, K.; Simell, P. [VTT Processes, P.O. Box 1601, FIN-02044 VTT (Finland)

    2003-07-01

    Alumina-supported catalysts containing different transition metals (Ni, Cu, Cr, Mn, Fe and Co) were prepared and tested for their activity in the selective oxidation of ammonia reaction at high temperatures (between 700 and 900C) using a synthetic gasification gas mixture. The catalysts were also characterised for their acidic properties by infrared studies of pyridine and ammonia adsorption and reaction/desorption. The Ni/Al{sub 2}O{sub 3} and Cr/Al{sub 2}O{sub 3} catalyst displayed the highest selective catalytic oxidation (SCO) activity in that temperature range with excellent N{sub 2} selectivities. FT-IR studies of adsorbed pyridine and NH{sub 3} indicate that Lewis acid sites dominate and that NH{sub 3} adsorption on these sites is likely to be the first step in the SCO reaction. FT-IR studies on less active catalysts, particularly on Cu/Al{sub 2}O{sub 3} allowed the detection of oxidation intermediates, amide (NH{sub 2}), and possibly hydrazine and imido and nitroxyl species. The amide and hydrazine intermediate gives credence to a proposed SCO mechanism involving a hydrazine intermediate, while the proposed imide, =N-H, and/or nitroxyl, HNO species could be intermediates in incomplete oxidation of NH{sub 3} to N{sub 2}O.

  16. Partial oxidation of landfill leachate in supercritical water: Optimization by response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Yanmeng; Wang, Shuzhong; Xu, Haidong; Guo, Yang; Tang, Xingying

    2015-09-15

    Highlights: • Partial oxidation of landfill leachate in supercritical water was investigated. • The process was optimized by Box–Behnken design and response surface methodology. • GY{sub H2}, TRE and CR could exhibit up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56%. • Small amounts of oxidant can decrease the generation of tar and char. - Abstract: To achieve the maximum H{sub 2} yield (GY{sub H2}), TOC removal rate (TRE) and carbon recovery rate (CR), response surface methodology was applied to optimize the process parameters for supercritical water partial oxidation (SWPO) of landfill leachate in a batch reactor. Quadratic polynomial models for GY{sub H2}, CR and TRE were established with Box–Behnken design. GY{sub H2}, CR and TRE reached up to 14.32 mmol·gTOC{sup −1}, 82.54% and 94.56% under optimum conditions, respectively. TRE was invariably above 91.87%. In contrast, TC removal rate (TR) only changed from 8.76% to 32.98%. Furthermore, carbonate and bicarbonate were the most abundant carbonaceous substances in product, whereas CO{sub 2} and H{sub 2} were the most abundant gaseous products. As a product of nitrogen-containing organics, NH{sub 3} has an important effect on gas composition. The carbon balance cannot be reached duo to the formation of tar and char. CR increased with the increase of temperature and oxidation coefficient.

  17. Influence of the Crystal Structure of Titanium Oxide on the Catalytic Activity of Rh/TiO2 in Steam Reforming of Propane at Low Temperature.

    Science.gov (United States)

    Yu, Lin; Sato, Katsutoshi; Toriyama, Takaaki; Yamamoto, Tomokazu; Matsumura, Syo; Nagaoka, Katsutoshi

    2018-05-01

    Solid oxide fuel cells (SOFCs) using liquefied petroleum gas(LPG) reduce CO2 emissions due to their high energy-conversion efficiency. Although SOFCs can convert LPG directly, coking occurs easily by decomposition of hydrocarbons, including C-C bonds on the electrode of fuel cell stacks. It is therefore necessary to develop an active steam pre-reforming catalyst that eliminates the hydrocarbons at low temperature, where waste heat of SOFCs is used. Here we show that the crystal structure of the TiO2 that anchors Rh particles is crucial for catalytic activity of Rh/TiO2 catalysts for propane pre-reforming. Our experimental results revealed that strong metal support interaction (SMSI) induced during H2 pre-reduction were optimized over Rh/TiO2 with a rutile structure; this catalyst catalyzed the reaction much more effectively than conventional Rh/γ-Al2O3. In contrast, the SMSI was too strong for Rh/TiO2 with an anatase structure, and the surface of the Rh particles was therefore covered mostly with partially reduced TiO2. The result was very low activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Atomic-Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation.

    Science.gov (United States)

    Melzer, Daniel; Xu, Pinghong; Hartmann, Daniela; Zhu, Yuanyuan; Browning, Nigel D; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-07-25

    Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M6 O21 units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation.

    Science.gov (United States)

    Işci, Umit; Afanasiev, Pavel; Millet, Jean-Marc M; Kudrik, Evgeny V; Ahsen, Vefa; Sorokin, Alexander B

    2009-09-28

    Mu-nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl) phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mössbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe(3.5)-N-Fe(3.5) structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe(IV)-N-Fe(IV) complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe(3.5)-N-Fe(3.5) unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 A and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 A. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by tBuOOH. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.

  20. Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes.

    Science.gov (United States)

    Doyle, Richard L; Godwin, Ian J; Brandon, Michael P; Lyons, Michael E G

    2013-09-07

    This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis - bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis.

  1. Catalytic reduction of 4-nitrophenol over Ni-Pd nanodimers supported on nitrogen-doped reduced graphene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Lijun, E-mail: liulj@wtu.edu.cn [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Chen, Ruifen; Liu, Weikai [College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, People' s Republic of China (China); Wu, Jiamin [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States); Gao, Di, E-mail: gaod@pitt.edu [Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

    2016-12-15

    Catalytic reduction of toxic 4-nitrophenol to 4-aminophenol over magnetically recoverable nanocatalysts has attracted much attention. Herein, we report a Ni-Pd/NrGO catalyst through the growth of Ni-Pd nanodimers (NDs) on nitrogen-doped reduced graphene oxide (NrGO). The Ni-Pd NDs show a heterogeneous nanostructure with Ni and Pd subparts contacting with each other, remarkably different from the frequently-observed core/shell nanoparticles (NPs) or nanoalloy. The formation of Ni-Pd NDs follows an initial deposition of Pd NPs on the graphene and in-situ catalytic generation of Ni subparts over the newly-generated Pd NPs. The resulting Ni-Pd/NrGO exhibits a superior catalytic activity towards the reduction of 4-nitrophenol at room temperature with a high rate constant (3400 s{sup -1} g{sup -1}) and a low activated energy (29.1 kJ mol{sup -1}) as compared to unsupported Ni-Pd NDs and supported monometallic catalysts. The conversion rate of 4-NP is calculated to be 99.5% and the percent yield (%) of 4-AP is as high as 99.1%. A synergistic catalysis mechanism is rationally proposed, which is ascribed to the electronic modification of Ni-Pd metals due to the strong metal/support interaction (SMSI) effect as well as the electron transfer between Ni and Pd. The hybrid catalyst shows soft ferromagnetic properties and can be magnetically separated and recycled without obvious loss of activity.

  2. Modification of Titanium Dioxide Nanoparticles With Copper Oxide Co-Catalyst for Photo catalytic Degradation of 2,4-Dichlorophenoxyacetic Acid

    International Nuclear Information System (INIS)

    Leny Yuliati; Siah, W.R.; Nur Azmina Roslan; Mustaffa Shamsuddin

    2016-01-01

    2,4-dichlorophenoxyacetic acid (2,4-D) is a common herbicide that has been used widely. Due to its excessive usage, the 2,4-D herbicides can cause contamination over agricultural land and water bodies. In the present work, a simple impregnation method was used to modify the commercial titanium dioxide (P25 TiO 2 ) nanoparticles with the copper oxide. The prepared samples were characterized by X-ray Diffraction (XRD), reflectance UV-visible and fluorescence spectroscopies. It was observed that the incorporation of copper oxide did not significantly affect the crystal structure of P25 TiO 2 . On the other hand, the presence of copper oxide was confirmed by reflectance UV-visible and fluorescence spectroscopies. The activity of the prepared sample was evaluated for photo catalytic removal of the 2,4-D. The photo catalytic activity of the TiO 2 increased with the increase of copper oxide loading up to 0.5 mol %. Unfortunately, the higher loading amount of copper oxide resulted in the lower photo catalytic activity. This study suggested that the higher photo catalytic activities obtained on the low loading samples were due to the lower electron-hole recombination. (author)

  3. Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

    2017-04-30

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  4. Co3O4-CeO2 mixed oxide-based catalytic materials for diesel soot oxidation

    Czech Academy of Sciences Publication Activity Database

    Dhakad, M.; Mitshuhashi, T.; Rayalu, S.; Doggali, P.; Bakardjieva, Snejana; Šubrt, Jan; Fino, D.; Haneda, H.; Labhsetwar, N.

    2008-01-01

    Roč. 132, 1-4 (2008), s. 188-193 ISSN 0920-5861 R&D Projects: GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : soot oxidation * diesel particulate * Co3O4-CeO2 type mixed oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 3.004, year: 2008

  5. Steam and partial oxidation reforming options for hydrogen production from fossil fuels for PEM fuel cells

    Directory of Open Access Journals (Sweden)

    Yousri M.A. Welaya

    2012-06-01

    Full Text Available Proton exchange membrane fuel cell (PEM generates electrical power from air and from hydrogen or hydrogen rich gas mixtures. Therefore, there is an increasing interest in converting current hydrocarbon based marine fuels such as natural gas, gasoline, and diesel into hydrogen rich gases acceptable to the PEM fuel cells on board ships. Using chemical flow sheeting software, the total system efficiency has been calculated. Natural gas appears to be the best fuel for hydrogen rich gas production due to its favorable composition of lower molecular weight compounds. This paper presents a study for a 250 kW net electrical power PEM fuel cell system utilizing a partial oxidation in one case study and steam reformers in the second. This study has shown that steam-reforming process is the most competitive fuel processing option in terms of fuel processing efficiency. Partial oxidation process has proved to posses the lowest fuel processing efficiency. Among the options studied, the highest fuel processing efficiency is achieved with natural gas steam reforming system.

  6. Synthesis, Characterization, and Relative Study on the Catalytic Activity of Zinc Oxide Nanoparticles Doped MnCO3, –MnO2, and –Mn2O3 Nanocomposites for Aerial Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Mohamed E. Assal

    2017-01-01

    Full Text Available Zinc oxide nanoparticles doped manganese carbonate catalysts [X% ZnOx–MnCO3] (where X = 0–7 were prepared via a facile and straightforward coprecipitation procedure, which upon different calcination treatments yields different manganese oxides, that is, [X% ZnOx–MnO2] and [X% ZnOx–Mn2O3]. A comparative catalytic study was conducted to evaluate the catalytic efficiency between carbonates and oxides for the selective oxidation of secondary alcohols to corresponding ketones using molecular oxygen as a green oxidizing agent without using any additives or bases. The prepared catalysts were characterized by different techniques such as SEM, EDX, XRD, TEM, TGA, BET, and FTIR spectroscopy. The 1% ZnOx–MnCO3 calcined at 300°C exhibited the best catalytic performance and possessed highest surface area, suggesting that the calcination temperature and surface area play a significant role in the alcohol oxidation. The 1% ZnOx–MnCO3 catalyst exhibited superior catalytic performance and selectivity in the aerial oxidation of 1-phenylethanol, where 100% alcohol conversion and more than 99% product selectivity were obtained in only 5 min with superior specific activity (48 mmol·g−1·h−1 and 390.6 turnover frequency (TOF. The specific activity obtained is the highest so far (to the best of our knowledge compared to the catalysts already reported in the literatures used for the oxidation of 1-phenylethanol. It was found that ZnOx nanoparticles play an essential role in enhancing the catalytic efficiency for the selective oxidation of alcohols. The scope of the oxidation process is extended to different types of alcohols. A variety of primary, benzylic, aliphatic, allylic, and heteroaromatic alcohols were selectively oxidized into their corresponding carbonyls with 100% convertibility without overoxidation to the carboxylic acids under base-free conditions.

  7. Active carbon-ceramic sphere as support of ruthenium catalysts for catalytic wet air oxidation (CWAO) of resin effluent.

    Science.gov (United States)

    Liu, Wei-Min; Hu, Yi-Qiang; Tu, Shan-Tung

    2010-07-15

    Active carbon-ceramic sphere as support of ruthenium catalysts were evaluated through the catalytic wet air oxidation (CWAO) of resin effluent in a packed-bed reactor. Active carbon-ceramic sphere and ruthenium catalysts were characterized by N(2) adsorption and chemisorption measurements. BET surface area and total pore volume of active carbon (AC) in the active carbon-ceramic sphere increase with increasing KOH-to-carbon ratio, and AC in the sample KC-120 possesses values as high as 1100 m(2) g(-1) and 0.69 cm(3) g(-1) (carbon percentage: 4.73 wt.%), especially. Active carbon-ceramic sphere supported ruthenium catalysts were prepared using the RuCl(3) solution impregnation onto these supports, the ruthenium loading was fixed at 1-5 wt.% of AC in the support. The catalytic activity varies according to the following order: Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>without catalysts. It is found that the 3 wt.% Ru/KC-120 catalyst displays highest stability in the CWAO of resin effluent during 30 days. Chemical oxygen demand (COD) and phenol removal were about 92% and 96%, respectively at the reaction temperature of 200 degrees C, oxygen pressure of 1.5 MPa, the water flow rate of 0.75 L h(-1) and the oxygen flow rate of 13.5 L h(-1). 2010 Elsevier B.V. All rights reserved.

  8. A facile and sensitive peptide-modulating graphene oxide nanoribbon catalytic nanoplasmon analytical platform for human chorionic gonadotropin.

    Science.gov (United States)

    Liang, Aihui; Li, Chongning; Li, Dan; Luo, Yanghe; Wen, Guiqing; Jiang, Zhiliang

    2017-01-01

    The nanogold reaction between HAuCl 4 and citrate is very slow, and the catalyst graphene oxide nanoribbon (GONR) enhanced the nanoreaction greatly to produce gold nanoparticles (AuNPs) that exhibited strong surface plasmon resonance (SPR) absorption (Abs) at 550 nm and resonance Rayleigh scattering (RRS) at 550 nm. Upon addition of the peptide of human chorionic gonadotropin (hCG), the peptide could adsorb on the GONR surface, which inhibited the catalysis. When hCG was added, peptides were separated from the GONR surface due to the formation of stable peptide-hCG complex, which led to the activation of GONR catalytic effect. With the increase in hCG concentration, the RRS and Abs signal enhanced linearly. The enhanced RRS value showed a good linear relationship with hCG concentration in the range of 0.2-20 ng/mL, with a detection limit of 70 pg/mL. Accordingly, two new GONR catalytic RRS/Abs methods were established for detecting hCG in serum samples.

  9. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    Science.gov (United States)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  10. Catalytic Reduction of Nitrous Oxide with Carbon Monoxide over Calcined Co–Mn–Al Hydrotalcite

    Czech Academy of Sciences Publication Activity Database

    Pacultová, K.; Obalová, L.; Kovanda, F.; Jirátová, Květa

    2008-01-01

    Roč. 137, 2-4 (2008), s. 358-389 ISSN 0920-5861 R&D Projects: GA ČR(CZ) GA106/05/0366 Institutional research plan: CEZ:AV0Z40720504 Keywords : nitrous oxide * carbon monoxide * mixed oxide catalysts Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.004, year: 2008

  11. Alumina supported Co-K-Mo based catalytic material for diesel soot oxidation

    Czech Academy of Sciences Publication Activity Database

    Dhakad, M.; Joshi, A.G.; Rayalu, S.; Tanwar, P.; Bassin, J.K.; Kumar, R.; Lokhande, S.; Šubrt, Jan; Mitsuhashi, T.; Labhsetwar, N.

    2009-01-01

    Roč. 52, 13-20 (2009), s. 2070-2075 ISSN 1022-5528 Institutional research plan: CEZ:AV0Z40320502 Keywords : soot oxidation * diesel particulate filter * catalyst carbon oxidation Subject RIV: CA - Inorganic Chemistry Impact factor: 2.379, year: 2009

  12. Importance of the oxygen bond strength for catalytic activity in soot oxidation

    DEFF Research Database (Denmark)

    Christensen, Jakob M.; Grunwaldt, Jan-Dierk; Jensen, Anker D.

    2016-01-01

    energies for soot oxidation follow linear Brønsted-Evans-Polanyi relationships with the heat of oxygen chemisorption. Among the tested metal or metal oxide catalysts Co3O4 and CeO2 were nearest to the optimal bond strength in tight contact oxidation, while Cr2O3 was nearest to the optimum in loose contact......The oxygen bond strength on a catalyst, as measured by the heat of oxygen chemisorption, is observed to be a very important parameter for the activity of the catalyst in soot oxidation. With both intimate contact between soot and catalyst (tight contact) and with the solids stirred loosely together...... oxidation. The optimum of the volcano curve in loose contact is estimated to occur between the bond strengths of α-Fe2O3 and α-Cr2O3. Guided by an interpolation principle FeaCrbOx binary oxides were tested, and the activity of these oxides was observed to pass through an optimum for an FeCr2Ox binary oxide...

  13. Synthesis, Characterization and Catalytic Performance in the Selective Oxidation of Alcohols by Metallophthalocyanines Supported on Zinc Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Amin Ebadi

    2017-01-01

    Full Text Available Unsubstituted phthalocyanines of Co, Fe and Mn supported on zinc oxide nanoparticles were prepared and were well characterized with X-ray diffraction and scanning electron microscopy. The oxidation of alcohols with tert-butylhydroperoxide, in the presence of metallophthalocyanines supported on zinc oxide nanoparticles was investigated. These MPc/ZnO nanocomposites were effective catalysts for the oxidation of alcohols such as cyclohexanol (83.4% conversion; 100% selectivity, benzyl alcohol (70.5% conversion; 100% selectivity and hexanol (62.3% conversion; 100% selectivity. The influences of reaction time, various metals and type of substrates and oxidants on the oxidation of alcohols were also studied, and optimized conditions were investigated. Under these reaction conditions, the activity of the catalysts decreases in the following order:  CoPc/nano-ZnO > FePc/nano-ZnO > MnPc/nano-ZnO. It shows that TBHP is more efficient oxidant due to weaker O-O bond with respect to H2O2 and the following order has been observed for the percentage of conversions of alcohols: 2º > benzylic > 1º.

  14. A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Jafarian, M.; Mahjani, M.G.; Heli, H.; Gobal, F.; Khajehsharifi, H.; Hamedi, M.H.

    2003-01-01

    Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour

  15. Preparation of mesoporous alumina films by anodization: Effect of pretreatments on the aluminum surface and MTBE catalytic oxidation

    International Nuclear Information System (INIS)

    Vazquez, A.L.; Carrera, R.; Arce, E.; Castillo, N.; Castillo, S.; Moran-Pineda, M.

    2009-01-01

    Mesoporous materials are both scientifically and technologically important because of the presence of voids of controllable dimensions at atomic, molecular, and nanometric scales. Over the last decade, there has been both an increasing interest and research effort in the synthesis and characterization of these types of materials. The purposes of this work are to study the physical and chemical changes in the properties of mesoporous alumina films produced by anodization in sulphuric acid by different pretreatments on the aluminium surface such as mechanical polishing [MP] and electropolishing [EP]; and to compare their properties such as morphology, structure and catalytic activity with those present in commercial alumina. The morphologic and physical characterizations of the alumina film samples were carried out by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical evaluations were performed by the oxidation of methyl-tert-butyl-ether (MTBE) at 400 deg. C under O 2 /He oxidizing conditions (Praxair, 2.0% O 2 /He balance). According to the results, the samples that presented higher activities than those in Al 2 O 3 /Al [MP] and commercial alumina in the MTBE oxidation (69%), were those prepared by Al 2 O 3 /Al [EP]. The average mesoporous diameter was 17 nm, and the morphological shape was equiaxial; thus, that pore distribution was the smallest of all with a homogeneous distribution.

  16. Model-based design of low-temperature carbon nanotube synthesis via catalytic oxidation for supercapacitor application.

    Science.gov (United States)

    Vasenkov, A V; Carnahan, D L

    2010-12-01

    Novel electrochemical double layer capacitors with carbon nanotube (CNT) electrode, often referred to as supercapacitors, have a potential to bridge a power and energy gap between traditional dielectric capacitors and chemical batteries. However, their future is uncertain because current fabrication technologies involve difficult-to-control post-growth manipulations of CNTs. This paper addresses this problem by introducing model-based design of low-temperature CNT synthesis that is suitable for in-situ fabrication of CNT-based supercapacitor electrode. The insight to the surface kinetics during low-temperature CNT synthesis via catalytic oxidation was obtained via coupled Molecular Dynamics and Quantum Semiempirical Hamiltonian simulations. It was determined that the presence of oxygen on the surface of catalyst increases, by several times, the time necessary for the decomposition of hydrocarbons as well as shifts the reaction zone from the surface of catalyst to the catalyst underlayer. Theoretical trends were confirmed by CNT growth experiments. A contact between conducting CNTs and zinc oxide binding layer was analyzed in detail since its properties strongly affect the performance of CNT electrode. It was demonstrated that the formed CNT-zinc oxide interface was free from unbonded oxygen atoms and/or clusters of zinc atoms and was weakly affected by defects in CNTs.

  17. Preparation of mesoporous alumina films by anodization: Effect of pretreatments on the aluminum surface and MTBE catalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Vazquez, A.L., E-mail: avazquezd@ipn.m [Departamento de Ingenieria Metalurgica, ESIQIE-IPN, AP 75-876, Mexico, D.F. (Mexico); Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, C.P. 07730, Mexico, D.F. (Mexico); Carrera, R. [Departamento de Ingenieria Metalurgica, ESIQIE-IPN, AP 75-876, Mexico, D.F. (Mexico); Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, C.P. 07730, Mexico, D.F. (Mexico); Arce, E. [Departamento de Ingenieria Metalurgica, ESIQIE-IPN, AP 75-876, Mexico, D.F. (Mexico); Castillo, N. [CINVESTAV, Departamento de Fisica. Av. IPN 2508, 07360, Mexico, D.F (Mexico); Castillo, S. [Departamento de Ingenieria Metalurgica, ESIQIE-IPN, AP 75-876, Mexico, D.F. (Mexico); Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, C.P. 07730, Mexico, D.F. (Mexico); Moran-Pineda, M. [Programa de Ingenieria Molecular, Instituto Mexicano del Petroleo, Eje Lazaro Cardenas 152, C.P. 07730, Mexico, D.F. (Mexico)

    2009-08-26

    Mesoporous materials are both scientifically and technologically important because of the presence of voids of controllable dimensions at atomic, molecular, and nanometric scales. Over the last decade, there has been both an increasing interest and research effort in the synthesis and characterization of these types of materials. The purposes of this work are to study the physical and chemical changes in the properties of mesoporous alumina films produced by anodization in sulphuric acid by different pretreatments on the aluminium surface such as mechanical polishing [MP] and electropolishing [EP]; and to compare their properties such as morphology, structure and catalytic activity with those present in commercial alumina. The morphologic and physical characterizations of the alumina film samples were carried out by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical evaluations were performed by the oxidation of methyl-tert-butyl-ether (MTBE) at 400 deg. C under O{sub 2}/He oxidizing conditions (Praxair, 2.0% O{sub 2}/He balance). According to the results, the samples that presented higher activities than those in Al{sub 2}O{sub 3}/Al [MP] and commercial alumina in the MTBE oxidation (69%), were those prepared by Al{sub 2}O{sub 3}/Al [EP]. The average mesoporous diameter was 17 nm, and the morphological shape was equiaxial; thus, that pore distribution was the smallest of all with a homogeneous distribution.

  18. Preparation of AuNPs/GQDs/SiO2 Composite and Its Catalytic Performance in Oxidation of Veratryl Alcohol

    Directory of Open Access Journals (Sweden)

    Yaoyao Yang

    2017-01-01

    Full Text Available Composites of gold nanoparticles and graphene quantum dots (AuNPs/GQDs exhibit excellent dispersibility in aqueous solutions. Thus, it is difficult to separate them from wet reaction systems when they are used as catalysts. To resolve this issue, in this study, an AuNPs/GQDs composite was immobilized on silicon dioxide through the hydrothermal method, which involved the formation of an amide bond between the surface GQDs of the AuNPs/GQDs composite and the amino group of the silane. The as-synthesized AuNPs/GQDs/SiO2 composite was found to be suitable for use as a heterogeneous catalyst for the oxidation of veratryl alcohol in water and exhibited catalytic activity comparable to that of bare AuNPs/GQDs as well as better recyclability.

  19. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  20. Free-Standing Metal Oxide Nanoparticle Superlattices Constructed with Engineered Protein Containers Show in Crystallo Catalytic Activity.

    Science.gov (United States)

    Lach, Marcel; Künzle, Matthias; Beck, Tobias

    2017-12-11

    The construction of defined nanostructured catalysts is challenging. In previous work, we established a strategy to assemble binary nanoparticle superlattices with oppositely charged protein containers as building blocks. Here, we show that these free-standing nanoparticle superlattices are catalytically active. The metal oxide nanoparticles inside the protein scaffold are accessible for a range of substrates and show oxidase-like and peroxidase-like activity. The stable superlattices can be reused for several reaction cycles. In contrast to bulk nanoparticle-based catalysts, which are prone to aggregation and difficult to characterize, nanoparticle superlattices based on engineered protein containers provide an innovative synthetic route to structurally defined heterogeneous catalysts with control over nanoparticle size and composition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...... and Pt are the best direct NO decomposition catalysts among the 3d, 4d, and 5d metals. We analyze the NO decomposition reaction in terms of the Sabatier analysis and a Sabatier–Gibbs-type analysis and obtain an activity trend in agreement with experimental results. 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. We calculate adsorption and transition state energies for the full CO oxidation reaction pathway by the use of DFT for a number...

  2. Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

    International Nuclear Information System (INIS)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun

    2011-01-01

    We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates

  3. Advanced oxidation removal of hypophosphite by O3/H2O2 combined with sequential Fe(II) catalytic process.

    Science.gov (United States)

    Zhao, Zilong; Dong, Wenyi; Wang, Hongjie; Chen, Guanhan; Wang, Wei; Liu, Zekun; Gao, Yaguang; Zhou, Beili

    2017-08-01

    Elimination of hypophosphite (HP) was studied as an example of nickel plating effluents treatment by O 3 /H 2 O 2 and sequential Fe(II) catalytic oxidation process. Performance assessment performed with artificial HP solution by varying initial pH and employing various oxidation processes clearly showed that the O 3 /H 2 O 2 ─Fe(II) two-step oxidation process possessed the highest removal efficiency when operating under the same conditions. The effects of O 3 dosing, H 2 O 2 concentration, Fe(II) addition and Fe(II) feeding time on the removal efficiency of HP were further evaluated in terms of apparent kinetic rate constant. Under improved conditions (initial HP concentration of 50 mg L -1 , 75 mg L -1 O 3 , 1 mL L -1 H 2 O 2 , 150 mg L -1 Fe(II) and pH 7.0), standard discharge (<0.5 mg L -1 in China) could be achieved, and the Fe(II) feeding time was found to be the limiting factor for the evolution of apparent kinetic rate constant in the second stage. Characterization studies showed that neutralization process after oxidation treatment favored the improvement of phosphorus removal due to the formation of more metal hydroxides. Moreover, as a comparison with lab-scale Fenton approach, the O 3 /H 2 O 2 ─Fe(II) oxidation process had more competitive advantages with respect to applicable pH range, removal efficiency, sludge production as well as economic costs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water.

    Science.gov (United States)

    Ma, Wei; Zong, Panpan; Cheng, Zihong; Wang, Baodong; Sun, Qi

    2014-02-15

    This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid-solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH=7 with a 2:1 liquid-solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03-0.1 min(-1)) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH=7.0 compared with ozonation alone. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. The influence of the oxygen partial pressure on the quasi-ternary system Cr-Mn-Ti-oxide

    International Nuclear Information System (INIS)

    Garcia-Rosales, C.; Schulze, H.A.; Naoumidis, A.; Nickel, H.

    1991-05-01

    The passivation layers formed by the oxidizing corrosion of high temperature alloys consist primarily of oxides and mixed oxides of the elements chromium, manganese and titanium. For a reproducible formation and characterization of such oxide layers it is necessary to know the phase equilibria of these oxide systems at temperature and oxygen partial pressure conditions which will be relevant during their application. For the investigation of the quasi-ternary system Cr-Mn-Ti-oxide, oxide powders were prepared and annealed at 1000deg C under different oxygen partial pressures ranging from 0.21 bar to 10 -21 bar. Phase identification and determination of lattice parameter using X-ray diffraction analysis as well as the direct measurement of phase boundaries as a function of oxygen partial pressure using the emf-methode were carried out for these investigations. In the quasi-ternary system Cr-Mn-Ti-oxide the spinels play a decisive role in the oxigen partial pressure range examined. The spinel MnCr 2 O 4 may be regarded as the most significant compound. Part of the chronium can be replaced by trivalent manganese at high oxygen partial pressures and by trivalent titanium at low pressures, and the formation of a solid solution with the spinel Mn 2 TiO 4 is possible in all cases. In this way a coherent single-phase spinel region is observed which extends over the entire oxygen partial pressure range form 0.21 bar to 10 -21 bar examined at 1000deg C. (orig.) [de

  6. Influence of fuel properties, nitrogen oxides, and exhaust treatment by an oxidation catalytic converter on the mutagenicity of diesel engine emissions.

    Science.gov (United States)

    Bünger, Jürgen; Krahl, Jürgen; Weigel, Andreas; Schröder, Olaf; Brüning, Thomas; Müller, Michael; Hallier, Ernst; Westphal, Götz

    2006-08-01

    Particle emissions of diesel engines (DEP) content polycyclic aromatic hydrocarbons (PAH) these compounds cause a strong mutagenicity of solvent extracts of DEP. We investigated the influence of fuel properties, nitrogen oxides (NO( x )), and an oxidation catalytic converter (OCC) on the mutagenic effects of DEP. The engine was fuelled with common diesel fuel (DF), low-sulphur diesel fuel (LSDF), rapeseed oil methyl ester (RME), and soybean oil methyl ester (SME) and run at five different load modes in two series with and without installation of an OCC in the exhaust pipe. Particles from the cooled and diluted exhaust were sampled onto glass fibre filters and extracted with dichloromethane in a soxhlet apparatus. The mutagenicity of the extracts was tested using the Salmonella typhimurium/mammalian microsome assay with tester strains TA98 and TA100. Without OCC the number of revertant colonies was lower in extracts of LSDF than in extracts of DF. The lowest numbers of revertant colonies were induced by the plant oil derived fuels. In three load modes, operation with the OCC led to a reduction of the mutagenicity. However, direct mutagenic effects under heavy duty conditions (load mode A) were significantly increased for RME (TA98, TA100) and SME (TA98). A consistent but not significant increase in direct mutagenicity was observed for DF and LSDF at load mode A, and for DF at idling (load mode E) when emissions were treated with the OCC. These results raise concern over the use of oxidation catalytic converters with diesel engines. We hypothesise that the OCC increases formation of direct acting mutagens under certain conditions by the reaction of NO( x ) with PAH resulting in the formation of nitrated-PAH. Most of these compounds are powerful direct acting mutagens.

  7. Magnetic properties in a partially oxidized nanocomposite of Cu-CuCl

    International Nuclear Information System (INIS)

    Li Qi; Zhang Shiwei; Zhang Yan; Chen Chinping

    2006-01-01

    Magnetism of a very thin antiferromagnetic (AFM) surface CuO has been investigated with partially oxidized nanocomposites of Cu-CuCl, ∼200 nm. The samples are characterized by x-ray diffraction, x-ray photoelectron spectroscopy, x-ray-excited Auger electron spectroscopy, transmission electron microscopy and magnetic measurements. The characterizations indicate that the composites have a core-shell structure. Before oxidation, it is (Cu) core /(CuCl) shell , and after oxidation it is (Cu) core /(Cu 2 O+CuCl+minute CuO) shell . The magnetic measurements have revealed that a ferromagnetic (FM)-like open hysteresis exists at temperatures below the freezing point, T F . In the high field region, a paramagnetic (PM) response appears without showing any sign of saturation. Also, the field dependent magnetization (M-H) measurement is PM-like at T>T F . These interesting magnetic properties are shown to arise from the AFM CuO on the outer surface. They are attributed to the uncompensated surface spins of Cu 2+ and the effect of random surface potential. More interestingly, the magnetic susceptibility is greatly enhanced in the presence of Cl - anions at T F , according to the field-cooled/zero-field-cooled (FC/ZFC) measurements. This further supports the point that the disorder or frustration effect of the impurity would reduce the AFM ordering of CuO and increase the level of uncompensated spins

  8. Regimes of an atmospheric pressure nanosecond repetitively pulsed discharge for methane partial oxidation

    Science.gov (United States)

    Maqueo, P. D. G.; Maier, M.; Evans, M. D. G.; Coulombe, S.; Bergthorson, J. M.

    2018-04-01

    The operation of a nanosecond repetitively pulsed discharge for partial oxidation of CH4 is characterized at atmospheric pressure and room temperature. Two regimes are observed: diffuse and filamentary. The first is a low power regime, characterized by low rotational temperatures around 400 K. The second is much more energetic with rotational temperatures close to 600 K. Both have vibrational temperatures of at least 10 times their rotational temperatures. The average electron number density was determined to be 8.9×1015 and 4.0×1017 cm-3, respectively, showing an increase in the ionization fraction in the more powerful filamentary regime. Results of CH4 conversion to H2, CO, CO2 and C2H6 are presented for the filamentary regime, while the diffuse regime shows no measurable conversion ability. As expected, oxidative mixtures show higher conversion ability than pure CH4. A maximum conversion efficiency of 26.3% and a maximum energy efficiency of 19.7% were reached for the oxidative mixtures.

  9. Partial oxidation of sewage sludge briquettes in a updraft fixed bed.

    Science.gov (United States)

    Kim, Minsu; Lee, Yongwoon; Park, Jinje; Ryu, Chankook; Ohm, Tae-In

    2016-03-01

    The fixed bed reaction of sewage sludge briquettes was investigated to evaluate the potential applications to gasification, combustion, or production of biochar as soil ameliorator. The reaction had two distinctive stages: ignition propagation and char oxidation. The ignition front of the sludge briquettes propagated at a lower speed, which significantly increased the stoichiometric ratio of overall combustion reaction and peak temperatures. The ignition front also had irregular shapes due to the channeling effects. During the char oxidation stage, the sludge ash agglomerated because of the slow reaction rate and increased CO2 formation. Because of low energy content in the product gas, the large briquettes were not favorable for syngas production. In addition, the low burning rates and ash agglomeration could cause problems in the operation of a grate-type furnace for combustion. However, the char accumulated above the ignition front had similar properties with that from pyrolysis under inert atmosphere. Therefore, the fixed bed reaction under partial oxidation conditions can be applied to produce biochar as soil ameliorator from the sludge briquettes without external heat supply. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Catalytic activity of CuO-Gd0.1Ti0.1Zr0.1Ce0.7O2 in CO oxidation

    Indian Academy of Sciences (India)

    after accounting for instrumental broadening using ger- manium as reference. Quantitative phase analysis was ... with an X-ray microanalysis system INCA Energy 350. (Oxford Instruments). The catalytic activity of the synthesized samples in the oxidation of CO was determined by the flow method at atmospheric pressure.

  11. A new 3-D open-framework cadmium borovanadate with plane-shaped channels and high catalytic activity for the oxidation of cyclohexanol.

    Science.gov (United States)

    Feng, Yuquan; Qiu, Dongfang; Fan, Huitao; Li, Min; Huang, Qunzeng; Shi, Hengzhen

    2015-05-21

    A new 3-D open-framework cadmium borovanadate with 6-connected topology was hydrothermally obtained and structurally characterized. It not only features new cadmium(II) borovanadate which possesses an open-framework structure with unique plane-shaped channels, but also exhibits interesting absorption properties and high catalytic activities for the oxidation of cyclohexanol.

  12. 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......-removal in flue-gas cleaning from waste incineration....

  13. Molybdenum-based additives to mixed-metal oxides for use in hot gas cleanup sorbents for the catalytic decomposition of ammonia in coal gases

    Science.gov (United States)

    Ayala, Raul E.

    1993-01-01

    This invention relates to additives to mixed-metal oxides that act simultaneously as sorbents and catalysts in cleanup systems for hot coal gases. Such additives of this type, generally, act as a sorbent to remove sulfur from the coal gases while substantially simultaneously, catalytically decomposing appreciable amounts of ammonia from the coal gases.

  14. Production of C(3)/C(4) Olefins from n-Hexane: Conceptual design of a catalytic oxidative cracking process and comparison to steam cracking

    NARCIS (Netherlands)

    Boyadjian, C.A.; Seshan, Kulathuiyer; Lefferts, Leonardus; van der Ham, Aloysius G.J.; van den Berg, Henderikus

    2011-01-01

    A conceptual design of the catalytic oxidative cracking (COC) of hexane as a model compound of naphtha is reported. The design is based on experimental data which are elaborated through a structural design method to a process flow sheet. The potential of COC as an alternative to steam cracking (SC)

  15. Catalytic oxidation of olefins and sulfides in the presence of hydrazone-oxidovanadium(V) complex containing VOCl.sub.2./sub..sup.+./sup. core

    Czech Academy of Sciences Publication Activity Database

    Bikas, R.; Ghorbanloo, M.; Jafari, S.; Eigner, Václav; Dušek, Michal

    2016-01-01

    Roč. 453, Nov (2016), s. 78-85 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA14-03276S; GA MŠk LO1603 Institutional support: RVO:68378271 Keywords : oxidovanadium(V) * catalytic oxidation * hydrazone ligand * crystal structure * VOCl 2 + Subject RIV: CA - Inorganic Chemistry Impact factor: 2.002, year: 2016

  16. Corrigendum to Photo catalytic Oxidation of Trichloroethylene in Water Using a Porous Ball of Nano-Zn O and Nano clay Composite

    International Nuclear Information System (INIS)

    Bak, S. A.; Song, M. S.; Nam, I.T.; Lee, W.G.

    2015-01-01

    In the published paper entitled Photo catalytic Oxidation of Trichloroethylene in Water Using a Porous Ball of Nano-Zn O and Nano clay Composite [1], we mistakenly used Laponite in our paper. The corrected name is Laponite (BYK Corporations products). So we are making some changes from Laponite to Laponite (BYK Corporations products) in our paper.

  17. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Science.gov (United States)

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  18. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    Science.gov (United States)

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  19. A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation. Annual progress report, September 15, 1996 - September 14, 1997

    International Nuclear Information System (INIS)

    Sen, A.

    1997-01-01

    'During the first year, the palladium-catalyzed deep oxidation of toxic organics by dioxygen in aqueous solution was examined in some detail. The research performed has established the viability of the catalytic system to effect the deep (and complete) oxidation of a very wide range of organic substrates under mild conditions. One significant observation was that chemical warfare agent models containing phosphorus-carbon and sulfur-carbon bonds could be eliminated by using this procedure.'

  20. Homogeneous catalytic systems for selective oxidation of methane: state of the art

    Directory of Open Access Journals (Sweden)

    Balcer Sylwia

    2015-09-01

    Full Text Available Homogeneous catalysts for methane oxidation are of a particular interest from scientific and economic points of view. The results show a great potential for activation and functionalization of CH bonds of unreactive methane. There are still gaps in the knowledge of how to rationally design catalysts for this process. In this paper state-of-the-art. in methane oxidation homogenous catalysis is presented.

  1. Enhanced activity and stability of copper oxide/γ-alumina catalyst in catalytic wet-air oxidation: Critical roles of cerium incorporation

    Science.gov (United States)

    Zhang, Yongli; Zhou, Yanbo; Peng, Chao; Shi, Junjun; Wang, Qingyu; He, Lingfeng; Shi, Liang

    2018-04-01

    By successive impregnation method, the Ce-modified Cu-O/γ-Al2O3 catalyst was prepared and characterized using nitrogen adsorption-desorption, scanning electron microscopy energy dispersive X-ray analysis (SEM-EDS), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, and H2-Temperature programming reduction (H2-TPR). In catalytic wet-air oxidation (CWAO) process for the printing and dyeing wastewater (PDW), the effects of Ce addition on performance, mechanism and kinetics of the catalyst were investigated. The Ce addition increases the Brunauer-Emmett-Teller (BET) surface area and pore volume of the catalyst and makes the active components uniformly distributed on the catalyst surface. Formation of a stable CuAl2O4 solid solution by anchoring Cu onto the γ-Al2O3 crystal lattice leads to a significant decrease in metal leaching of the Ce-modified catalyst. The proportion of lattice oxygen in the catalyst substantially increases and the apparent activation energy of Cu-O/γ-Al2O3 catalyst decreases owing to Ce addition. Therefore, the catalytic activity and stability of the Ce-modified catalyst are considerably improved. The scavengers experiments identify the active species existed in the CWAO reaction system, with the order of reactivity: h+ > O2•- > H2O2 > HO•. This novel Cu-Ce-O/γ-Al2O3 catalyst has great potential in applications for treatment of concentrated organic wastewater due to its superior catalytic activity and improved stability.

  2. Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields

    KAUST Repository

    Zhang, Jizhe

    2014-09-01

    Direct conversion of raw biomass materials to fine chemicals is of great significance from both economic and ecological perspectives. In this paper, we report that a Keggin-type vanadium-substituted phosphomolybdic acid catalyst, namely H4PVMo11O40, is capable of converting various biomass-derived substrates to formic acid and acetic acid with high selectivity in a water medium and oxygen atmosphere. Under optimized reaction conditions, H4PVMo11O40 gave an exceptionally high yield of formic acid (67.8%) from cellulose, far exceeding the values achieved in previous catalytic systems. Our study demonstrates that heteropoly acids are generally effective catalysts for biomass conversion due to their strong acidities, whereas the composition of metal addenda atoms in the catalysts has crucial influence on the reaction pathway and the product selectivity. © 2013 Elsevier B.V.

  3. Cobalt-manganese-based spinels as multifunctional materials that unify catalytic water oxidation and oxygen reduction reactions.

    Science.gov (United States)

    Menezes, Prashanth W; Indra, Arindam; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Strasser, Peter; Driess, Matthias

    2015-01-01

    Recently, there has been much interest in the design and development of affordable and highly efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts that can resolve the pivotal issues that concern solar fuels, fuel cells, and rechargeable metal-air batteries. Here we present the synthesis and application of porous CoMn2 O4 and MnCo2 O4 spinel microspheres as highly efficient multifunctional catalysts that unify the electrochemical OER with oxidant-driven and photocatalytic water oxidation as well as the ORR. The porous materials were prepared by the thermal degradation of the respective carbonate precursors at 400 °C. The as-prepared spinels display excellent performances in electrochemical OER for the cubic MnCo2 O4 phase in comparison to the tetragonal CoMn2 O4 material in an alkaline medium. Moreover, the oxidant-driven and photocatalytic water oxidations were performed and they exhibited a similar trend in activity to that of the electrochemical OER. Remarkably, the situation is reversed in ORR catalysis, that is, the oxygen reduction activity and stability of the tetragonal CoMn2 O4 catalyst outperformed that of cubic MnCo2 O4 and rivals that of benchmark Pt catalysts. The superior catalytic performance and the remarkable stability of the unifying materials are attributed to their unique porous and robust microspherical morphology and the intrinsic structural features of the spinels. Moreover, the facile access to these high-performance materials enables a reliable and cost-effective production on a large scale for industrial applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films

    KAUST Repository

    Sun, Ke

    2015-03-11

    Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g). © 2015, National Academy of Sciences. All rights reserved.

  5. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  6. Adiabatic Gasification and Pyrolysis of Coffee Husk Using Air-Steam for Partial Oxidation

    Directory of Open Access Journals (Sweden)

    Catalina Rodriguez

    2011-01-01

    Full Text Available Colombian coffee industry produces about 0.6 million tons of husk (CH per year which could serve as feedstock for thermal gasification to produce gaseous and liquid fuels. The current paper deals with: (i CH adiabatic gasification modeling using air-steam blends for partial oxidation and (ii experimental thermogravimetric analysis to determine the CH activation energy (E. The Chemical Equilibrium with Applications Program (CEA, developed by NASA, was used to estimate the effect of equivalence ratio (ER and steam to fuel ratio (S : F on equilibrium temperature and gas composition of ~150 species. Also, an atom balance model was developed for comparison purposes. The results showed that increased ER and (S : F ratios produce mixtures that are rich in H2 and CO2 but poor in CO. The value for the activation energy was estimated to be 221 kJ/kmol.

  7. Characteristic of nitrous oxide production in partial denitrification process with high nitrite accumulation.

    Science.gov (United States)

    Du, Rui; Peng, Yongzhen; Cao, Shenbin; Wang, Shuying; Niu, Meng

    2016-03-01

    Nitrous oxide (N2O) production during the partial denitrification process with nitrate (NO3(-)-N) to nitrite (NO2(-)-N) transformation ratio of 80% was investigated in this study. Results showed that N2O was seldom observed before complete depletion of NO3(-)-N, but it was closely related to the reduction of NO2(-)-N rather than NO3(-)-N. High COD/NO3(-)-N was in favor of N2O production in partial denitrification with high NO2(-)-N accumulation. It was seriously enhanced at constant acidic pH due to the free nitrous acid (FNA) inhibition. However, the N2O production was much lower at initial pH of 5.5 and 6.5 due to the pH increase during denitrification process. Significantly, the pH turning point could be chosen as a controlled parameter to denote the end of NO3(-)-N reduction, which could not only achieve high NO2(-)-N accumulation but also decrease the N2O production significantly for practical application. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO2

    International Nuclear Information System (INIS)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik; Hong, Jongki; Lee, Won Woong; Ryu, Jung Bok

    2017-01-01

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li a X a+1 ] − are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl − are non-corrosive under the carboxylation condition

  9. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik [Dept. of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, Seoul (Korea, Republic of); Hong, Jongki; Lee, Won Woong [College of Pharmacy, Kyung Hee University, Seoul (Korea, Republic of); Ryu, Jung Bok [R and D Center, Chuncheon (Korea, Republic of)

    2017-02-15

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li{sub a} X{sub a+1}]{sup −} are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl{sup −} are non-corrosive under the carboxylation condition.

  10. Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

    DEFF Research Database (Denmark)

    Madsen, Karin

    The vanadium-based SCR catalyst used for NOx-control promotes the oxidation of elemental mercury Hg0 to Hg2+ in flue gases from coal-fired power plants. Hg2+ is water soluble and can effectively be captured in a wet scrubber. This means that the combination of an SCR with a wet FGD can offer an e...

  11. Tuning size and catalytic activity of nano-clusters of cobalt oxide

    Indian Academy of Sciences (India)

    Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the ...

  12. Copper/ascorbic acid dyad as a catalytic system for selective aerobic oxidation of amines

    Czech Academy of Sciences Publication Activity Database

    Šrogl, Jiří; Voltrová, Svatava

    2009-01-01

    Roč. 11, č. 4 (2009), s. 843-845 ISSN 1523-7060 Institutional research plan: CEZ:AV0Z40550506 Keywords : copper * ascorbic acid * oxidative deamination Subject RIV: CC - Organic Chemistry Impact factor: 5.420, year: 2009

  13. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NARCIS (Netherlands)

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps:

  14. Electrochemical and density functional studies of the catalytic ethylene oxidation on nanostructured Au electrodes

    Czech Academy of Sciences Publication Activity Database

    Šebera, Jakub; Hoffmannová, Hana; Krtil, Petr; Samec, Zdeněk; Záliš, Stanislav

    2010-01-01

    Roč. 158, 1-2 (2010), s. 29-34 ISSN 0920-5861 R&D Projects: GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrocatalysis * ethylene oxidation * DFT Subject RIV: CG - Electrochemistry Impact factor: 2.993, year: 2010

  15. Influence of basic properties of Mg,Al-mixed oxides on their catalytic activity in knoevenagel condensation between benzaldehyde and phenylsulfonylacetonitrile

    Directory of Open Access Journals (Sweden)

    Caridad Noda Pérez

    2009-01-01

    Full Text Available The catalytic performance of Mg,Al-mixed oxides (MO20, MO25 and MO33 derived from hydrotalcites was evaluated in the Knoevenagel reaction between benzaldehyde and phenylsulfonylacetonitrile at 373 and 383 K. The best results were obtained for the sample MO20 that presented the highest basic sites density and external area and the smallest crystallite sizes. The relative amount of basic sites with weak to intermediate strength also played an important role on catalytic performance. By increasing the catalyst content from 1 to 5 wt.% at 383 K, a complete conversion of the reactants is attained, producing α-phenylsulfonylcinnamonitrile with a selectivity of 100%.

  16. Analysis of effect of flameholder characteristics on lean, premixed, partially vaporized fuel-air mixtures quality and nitrogen oxides emissions

    Science.gov (United States)

    Cooper, L. P.

    1981-01-01

    An analysis was conducted of the effect of flameholding devices on the precombustion fuel-air characteristics and on oxides of nitrogen (NOx) emissions for combustion of premixed partially vaporized mixtures. The analysis includes the interrelationships of flameholder droplet collection efficiency, reatomization efficiency and blockage, and the initial droplet size distribution and accounts for the contribution of droplet combustion in partially vaporized mixtures to NOx emissions. Application of the analytical procedures is illustrated and parametric predictions of NOx emissions are presented.

  17. Partial Oxidation Gas Turbine for Power and Hydrogen Co-Production from Coal-Derived Fuel in Industrial Applications

    Energy Technology Data Exchange (ETDEWEB)

    Joseph Rabovitser

    2009-06-30

    The report presents a feasibility study of a new type of gas turbine. A partial oxidation gas turbine (POGT) shows potential for really high efficiency power generation and ultra low emissions. There are two main features that distinguish a POGT from a conventional gas turbine. These are associated with the design arrangement and the thermodynamic processes used in operation. A primary design difference of the POGT is utilization of a non?catalytic partial oxidation reactor (POR) in place of a conventional combustor. Another important distinction is that a much smaller compressor is required, one that typically supplies less than half of the air flow required in a conventional gas turbine. From an operational and thermodynamic point of view a key distinguishing feature is that the working fluid, fuel gas provided by the OR, has a much higher specific heat than lean combustion products and more energy per unit mass of fluid can be extracted by the POGT expander than in the conventional systems. The POGT exhaust stream contains unreacted fuel that can be combusted in different bottoming ycle or used as syngas for hydrogen or other chemicals production. POGT studies include feasibility design for conversion a conventional turbine to POGT duty, and system analyses of POGT based units for production of power solely, and combined production of power and yngas/hydrogen for different applications. Retrofit design study was completed for three engines, SGT 800, SGT 400, and SGT 100, and includes: replacing the combustor with the POR, compressor downsizing for about 50% design flow rate, generator replacement with 60 90% ower output increase, and overall unit integration, and extensive testing. POGT performances for four turbines with power output up to 350 MW in POGT mode were calculated. With a POGT as the topping cycle for power generation systems, the power output from the POGT ould be increased up to 90% compared to conventional engine keeping hot section temperatures

  18. SUPERCRITICAL WATER PARTIAL OXIDATION PHASE I - PILOT-SCALE TESTING / FEASIBILITY STUDIES FINAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    SPRITZER,M; HONG,G

    2005-01-01

    Under Cooperative Agreement No. DE-FC36-00GO10529 for the Department of Energy, General Atomics (GA) is developing Supercritical Water Partial Oxidation (SWPO) as a means of producing hydrogen from low-grade biomass and other waste feeds. The Phase I Pilot-scale Testing/Feasibility Studies have been successfully completed and the results of that effort are described in this report. The Key potential advantages of the SWPO process is the use of partial oxidation in-situ to rapidly heat the gasification medium, resulting in less char formation and improved hydrogen yield. Another major advantage is that the high-pressure, high-density aqueous environment is ideal for reaching and gasifying organics of all types. The high water content of the medium encourages formation of hydrogen and hydrogen-rich products and is especially compatible with high water content feeds such as biomass materials. The high water content of the medium is also effective for gasification of hydrogen-poor materials such as coal. A versatile pilot plant for exploring gasification in supercritical water has been established at GA's facilities in San Diego. The Phase I testing of the SWPO process with wood and ethanol mixtures demonstrated gasification efficiencies of about 90%, comparable to those found in prior laboratory-scale SCW gasification work carreid out at the University of Hawaii at Manoa (UHM) as well as other biomass gasification experience with conventional gasifiers. As in the prior work at UHM, a significant amount of the hydrogen found in the gas phase products is derived from the water/steam matrix. The studies at UHM utilized an indirectly heated gasifier with an acitvated carbon catalyst. In contrast, the GA studies utilized a directly heated gasifier without catalyst, plus a surrogate waste fuel. Attainment of comparable gasification efficiencies without catalysis is an important advancement for the GA process, and opens the way for efficient hydrogen production from low

  19. Catalyst development and systems analysis of methanol partial oxidation for the fuel processor - fuel cell integration

    Energy Technology Data Exchange (ETDEWEB)

    Newson, E.; Mizsey, P.; Hottinger, P.; Truong, T.B.; Roth, F. von; Schucan, Th.H. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Methanol partial oxidation (pox) to produce hydrogen for mobile fuel cell applications has proved initially more successful than hydrocarbon pox. Recent results of catalyst screening and kinetic studies with methanol show that hydrogen production rates have reached 7000 litres/hour/(litre reactor volume) for the dry pox route and 12,000 litres/hour/(litre reactor volume) for wet pox. These rates are equivalent to 21 and 35 kW{sub th}/(litre reactor volume) respectively. The reaction engineering problems remain to be solved for dry pox due to the significant exotherm of the reaction (hot spots of 100-200{sup o}C), but wet pox is essentially isothermal in operation. Analyses of the integrated fuel processor - fuel cell systems show that two routes are available to satisfy the sensitivity of the fuel cell catalysts to carbon monoxide, i.e. a preferential oxidation reactor or a membrane separator. Targets for individual system components are evaluated for the base and best case systems for both routes to reach the combined 40% efficiency required for the integrated fuel processor - fuel cell system. (author) 2 figs., 1 tab., 3 refs.

  20. Sustainable hydrogen production by ethanol steam reforming using a partially reduced copper-nickel oxide catalyst.

    Science.gov (United States)

    Chen, Li-Chung; Cheng, Hongkui; Chiang, Chih-Wei; Lin, Shawn D

    2015-05-22

    Hydrogen production through the use of renewable raw materials and renewable energy is crucial for advancing its applications as an energy carrier. In this study, we fabricated a solid oxide solution of Cu and Ni within a confined pore space, followed by a partial reduction, to produce a highly efficient catalyst for ethanol steam reforming (ESR). At 300 °C, EtOH is completely converted, a H2 yield of approximately 5 mol per mol is achieved, and CO2 is the main carbon-containing product. This demonstrates that H2 production from bioethanol is an efficient and sustainable approach. Such a highly efficient ESR catalyst is attributed to the ability of the metal-oxide interface to facilitate the transformation of CHx adspecies from acetaldehyde decomposition into methoxy-like adspecies, which are reformed readily to produce H2 and consequently reduce CH4 formation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.