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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. Thermodynamic Study on the Catalytic Partial Oxidation of Methane to Syngas

    Institute of Scientific and Technical Information of China (English)

    XUJian; WEIWeisheng; 等

    2002-01-01

    The catalytic partial oxidation of methane to syngas (CO+H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.

  4. 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 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....

  5. 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)

  6. Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

    Science.gov (United States)

    Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

    It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

  7. 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....

  8. 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.)

  9. Catalytic ring-​opening copolymerization of limonene oxide and phthalic anhydride : toward partially renewable polyesters

    NARCIS (Netherlands)

    Hosseini Nejad, E.; Pionasari, A; Melis, van C.G.W.; Koning, C.E.; Duchateau, R.

    2013-01-01

    Catalytic ring-¿opening copolymn. of limonene oxide with phthalic anhydride was performed applying metal t-¿Bu-¿salophen complexes (t-¿Bu-¿salophen)¿MX; M = Cr, X = Cl (1)¿, M = Al, X = Cl (2)¿, M = Co, X = OAc (3)¿, M = Mn, X = Cl (4)¿, t-¿Bu-¿salophen =

  10. 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

    oxidation of methane, the catalyst reduced from the end to the beginning of the catalyst bed and oxidized again toward the end as soon as the entire catalyst bed was reduced. On an entirely oxidized catalyst bed, only total oxidation of methane was observed and consumed the oxygen until the conditions...... of the Pd particles at increasing age of the catalyst was observed, which leads to a lower oscillation frequency. Effects of particle size, oven temperature, and oxygen/methane ratio on the oscillation behavior were studied in detail. The deactivation period (reoxidation of Pd) was much less influenced...... 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....

  11. Study of the dynamics of the MoO2-Mo2C system for catalytic partial oxidation reactions

    Science.gov (United States)

    Cuba Torres, Christian Martin

    On a global scale, the energy demand is largely supplied by the combustion of non-renewable fossil fuels. However, their rapid depletion coupled with environmental and sustainability concerns are the main drivers to seek for alternative energetic strategies. To this end, the sustainable generation of hydrogen from renewable resources such as biodiesel would represent an attractive alternative solution to fossil fuels. Furthermore, hydrogen's lower environmental impact and greater independence from foreign control make it a strong contender for solving this global problem. Among a wide variety of methods for hydrogen production, the catalytic partial oxidation offers numerous advantages for compact and mobile fuel processing systems. For this reaction, the present work explores the versatility of the Mo--O--C catalytic system under different synthesis methods and reforming conditions using methyl oleate as a surrogate biodiesel. MoO2 exhibits good catalytic activity and exhibits high coke-resistance even under reforming conditions where long-chain oxygenated compounds are prone to form coke. Moreover, the lattice oxygen present in MoO2 promotes the Mars-Van Krevelen mechanism. Also, it is introduced a novel beta-Mo2C synthesis by the in-situ formation method that does not utilize external H2 inputs. Herein, the MoO 2/Mo2C system maintains high catalytic activity for partial oxidation while the lattice oxygen serves as a carbon buffer for preventing coke formation. This unique feature allows for longer operation reforming times despite slightly lower catalytic activity compared to the catalysts prepared by the traditional temperature-programmed reaction method. Moreover, it is demonstrated by a pulse reaction technique that during the phase transformation of MoO2 to beta-Mo2C, the formation of Mo metal as an intermediate is not responsible for the sintering of the material wrongly assumed by the temperature-programmed method.

  12. 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

  13. Fuel processor integrated H{sub 2}S catalytic partial oxidation technology for sulfur removal in fuel cell power plants

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, T.H.; Berry, D.A.; Lyons, K.D.; Beer, S.K.; Freed, A.D. [U.S. Department of Energy, Morgantown, WV (USA). National Energy Technology Laboratory

    2002-12-01

    H{sub 2}S catalytic partial oxidation technology with an activated carbon catalyst was found to be a promising method for the removal of hydrogen sulfide from fuel cell hydrocarbon feedstocks. Three different fuel cell feedstocks were considered for analysis: sour natural gas, sour effluent from a liquid middle distillate fuel processor and a Texaco O{sub 2}-blown coal-derived synthesis gas. The H{sub 2}S catalytic partial oxidation reaction, its integratability into fuel cell power plants with different hydrocarbon feedstocks and its salient features are discussed. Experimental results indicate that H{sub 2}S concentration can be removed down to the part-per-million level in these plants. Additionally, a power law rate expression was developed and reaction kinetics compared to prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H{sub 2}S and 0.3 order in O{sub 2}. 18 refs., 14 figs., 3 tabs.

  14. 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%

  15. A polygeneration from a dual-gas partial catalytic oxidation coupling with an oxygen-permeable membrane reactor

    International Nuclear Information System (INIS)

    Hao, Yanhong; Huang, Yi; Gong, Minhui; Li, Wenying; Feng, Jie; Yi, Qun

    2015-01-01

    Highlights: • A new polygeneration system (PL-PCO-OPMR) to DME/methanol/power is proposed. • Exergeo-economic analysis is adopted to disclose the performance of systems. • Key technological conditions and parameters for PL-PCO-OPMR are optimized. • PL-PCO-OPMR shows high energy efficiency and low CO_2 emission. • PL-PCO-OPMR is an attractive way for high efficient and clean use of COG and CGG. - Abstract: Polygeneration system, typically involving chemicals/fuels and electricity co-production, is a promising technology for the sustainable development of energy and environment. In this study, a new polygeneration system based on coal and coke oven gas (COG) inputs for co-production of dimethyl ether (DME)/methanol and electricity is proposed. In the new system, an appropriate syngas for the synthesis of DME is from coal gasified gas (CGG) reforming of COG coupled with an oxygen-permeable membrane reactor, in which both COG and CGG reforming process and fuel combustion process are incorporated, which reduces exergy destruction in the whole reforming process. In order to obtain the best performance of CO_2 reduction, energy saving and economic benefit, the key operation parameters of the proposed process are analyzed and optimized. The new system is compared with the process based on CH_4/CO_2 dry reforming, in terms of exergy efficiency, exergy cost and CO_2 emissions. Through the new system, the exergy efficiency can be increased by 7.8%, the exergy cost can be reduced by 0.88 USD/GJ and the CO_2 emission can be reduced by 0.023 kg/MJ. These results suggest that the polygeneration system from CGG and COG partial catalytic oxidation coupling with an oxygen-permeable membrane reactor (PL-PCO-OPMR) would be a more attractive way for highly efficient and clean use of CGG and COG.

  16. Phase composition and catalytic properties of oxide multicomponent molybdenum-containing catalysts for partial oxidation of propylene

    International Nuclear Information System (INIS)

    Malakhov, V.V.; Vlasov, A.A.; Boldyreva, N.N.; Dovlitova, L.S.; Plyasova, L.M.; Andrushkevich, T.V.; Kuznetsova, T.G.

    1996-01-01

    The catalytic properties and phase composition of multicomponent molybdenum-containing catalyst treated under various redox conditions have been studied. The phase composition has been considered by the methods of X-ray phase analysis and noncalibrated methods of differentiating dissolution (DD). Using the DD method the data on element composition, stoichiometry and quantitative content of phases of complex molybdates have been obtained for the first time. Data on modification of basic phases of the catalyst-cobalt and iron molybdates - by other cations from its composition suggest that the mechanism of action of the multicomponent catalyst is defined by the properties of one or several formed modified phases combining all the functions of an effective catalyst. 18 refs., 7 figs., 2 tabs

  17. Microwave-Assisted Coprecipitation Synthesis of LaCoO3 Nanoparticles and Their Catalytic Activity for Syngas Production by Partial Oxidation of Methane

    Directory of Open Access Journals (Sweden)

    Consuelo Alvarez-Galvan

    2018-04-01

    Full Text Available LaCoO3 perovskite-type oxides were prepared by microwave-assisted coprecipitation route and investigated in the catalytic partial oxidation of methane (CPOM to syngas. This preparation method aims to achieve higher specific surface areas (ssa than soft-chemical methods commonly used in the preparation of engineered materials. In an attempt to accomplish the creation of mesostructured porous LaCoO3, an ionic template such as cetyl trimethyl ammonium bromide has been used as endotemplate in some samples. The influence of pH and the type of precipitating agent has been studied. The materials have been characterized at different levels: morphology has been studied by scanning electron microscopy, textural properties by nitrogen adsorption–desorption at −196°C, structural analysis by X-ray diffraction, surface composition by X-ray photoelectron spectroscopy, thermal stability by thermogravimetric analysis, and carbon formation in spent catalysts by Raman spectroscopy. Structure-activity correlations point out that the precipitating agent has a key role on the morphology and porosity of the resultant oxide, as well as on the average crystalline domain of lanthanum perovskite (catalyst precursor. Thus, the use of ammonium hydroxide as precipitant leads to materials with a higher surface area and a greater ssa of cobalt (per unit mass, improving their catalytic performance for the CPOM reaction. The best catalytic performance was found for the catalyst prepared using ammonium hydroxide as precipitant (pH 9 and without adding CTAB as endotemplate.

  18. 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

  19. 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.

  20. 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.

  1. Catalytic oxidation using nitrous oxide

    Directory of Open Access Journals (Sweden)

    Juan Carlos Beltran-Prieto

    2017-01-01

    Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

  2. 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.)

  3. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

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

  4. 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.)

  5. 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.)

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

    Indian Academy of Sciences (India)

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

  7. Surface electronic structure-catalytic activity correlation of partially reduced molybdenum oxide(s) for the isomerization of light alkenes and alkanes

    International Nuclear Information System (INIS)

    Al-Kandari, S; Al-Kandari, H; Al-Kharafi, F; Katrib, A

    2008-01-01

    Catalytic activity-surface electronic structure correlation was carried out using surface XPS-UPS techniques. In situ reduction by hydrogen, were carried out at similar experimental conditions to those employed for the catalytic reactions. In the case of MoO 3 deposited on TiO 2 , the reduction to MoO 2 state with the bifunctional MoO 2 (H x ) ac phase on its surface starts at 573 K and reaches a stable state at temperatures between 653-673 K. In the case of alumina support, a strong metal-support interaction takes place during the catalyst preparation, leading to Al 2 (MoO 4 ) 3 complex formation as characterized by XRD. The reduction process(s) of this complex by hydrogen as a function of temperature is different from what is observed in the case of titania support. The changes in the chemical structure of the sample surface in both systems were tested for the catalytic reactions of 1-pentene and n-pentane

  8. Partial oxidation process

    International Nuclear Information System (INIS)

    Najjar, M.S.

    1987-01-01

    A process is described for the production of gaseous mixtures comprising H/sub 2/+CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, and vanadium-containing ash, or mixtures thereof. The feedstock includes a minimum of 0.5 wt. % of sulfur and the ash includes a minimum of 5.0 wt. % vanadium, a minimum of 0.5 ppm nickel, and a minimum of 0.5 ppm iron. The process comprises: (1) mixing together a copper-containing additive with the fuel feedstock; wherein the weight ratio of copper-containing additive to ash in the fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium; (2) reacting the mixture from (1) at a temperature in the range of 2200 0 F to 2900 0 F and a pressure in the range of about 5 to 250 atmospheres in a free-flow refactory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H/sub 2/+CO and entrained molten slag; and where in the reaction zone and the copper-containing additive combines with at least a portion of the nickel and iron constituents and sulfur found in the feedstock to produce a liquid phase washing agent that collects and transports at least a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory out of the reaction zone; and (3) separating nongaseous materials from the hot raw effluent gas stream

  9. Catalytic Oxidation of Cyanogen Chloride over a Monolithic Oxidation Catalyst

    National Research Council Canada - National Science Library

    Campbell, Jeffrey

    1997-01-01

    The catalytic oxidation of cyanogen chloride was evaluated over a monolithic oxidation catalyst at temperatures between 200 and 300 deg C in air employing feed concentrations between 100 and 10,000 ppm...

  10. Ni-doped (CeO{sub 2−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)

    Energy Technology Data Exchange (ETDEWEB)

    Somacescu, Simona, E-mail: ssimona@icf.ro [Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry (Romania); Florea, Mihaela [University of Bucharest, Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry (Romania); Osiceanu, Petre; Calderon-Moreno, Jose Maria [Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry (Romania); Ghica, Corneliu [National Institute of Materials Physics (Romania); Serra, Jose Manuel [Universidad Politécnica de Valencia - Consejo Superior de Investigaciones Científicas, Instituto de Tecnología Química (Spain)

    2015-11-15

    Ni-doped (CeO{sub 2−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). N{sub 2} 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 (Ce{sup 3+} + Ce{sup 4+}) with high percentage of Ce{sup 3+} valence state ∼35 % and (Ni{sup 3+} and Ni{sup 2+}) 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.Graphical Abstract.

  11. 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)

    International Nuclear Information System (INIS)

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

    2015-01-01

    Ni-doped (CeO 2−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). N 2 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 (Ce 3+  + Ce 4+ ) with high percentage of Ce 3+ valence state ∼35 % and (Ni 3+ and Ni 2+ ) 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.Graphical Abstract

  12. 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.

  13. Catalytic oxidation of cyclohexane to cyclohexanone

    Indian Academy of Sciences (India)

    ... a precursor and characterized by chemical analysis using the ICP–AES method, XRD, TEM, FTIR and BET surface area determination. The oxidation reaction was carried out at 70°C under atmospheric pressure. The results showed the catalytic performance of Pt/Al2O3 as being very high in terms of turnover frequency.

  14. Nitrogen removal from wastewater by a catalytic oxidation method.

    Science.gov (United States)

    Huang, T L; Macinnes, J M; Cliffe, K R

    2001-06-01

    The ammonia-containing waste produced in industries is usually characterized by high concentration and high temperature, and is not treatable by biological methods directly. In this study, a hydrophobic Pt/SDB catalyst was first used in a trickle-bed reactor to remove ammonia from wastewater. In the reactor, both stripping and catalytic oxidation occur simultaneously. It was found that higher temperature and higher oxygen partial pressure enhanced the ammonia removal. A reaction pathway, which involves oxidizing ammonia to nitric oxide, which then further reacts with ammonia to produce nitrogen and water, was confirmed. Small amounts of by-products, nitrites and nitrates were also detected in the resultant reaction solution. These compounds came from the absorption of nitrogen oxides. Both the minimum NO2- selectivity and maximum ammonia removal were achieved when the resultant pH of treated water was near 7.5 for a feed of unbuffered ammonia solution.

  15. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

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

    African Journals Online (AJOL)

    acer

    Kinetic Studies of Catalytic Oxidation of Cyclohexene Using Chromium VI Oxide in. Acetic Acid ... respect to the oxidant using pseudo-order approximation method. .... making the concentration of the cyclohexene in ..... on Titanium Silicate.

  17. 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.

  18. 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...

  19. ZVI (Fe0) desalination: catalytic partial desalination of saline aquifers

    Science.gov (United States)

    Antia, David D. J.

    2018-05-01

    Globally, salinization affects between 100 and 1000 billion m3 a-1 of irrigation water. The discovery that zero valent iron (ZVI, Fe0) could be used to desalinate water (using intra-particle catalysis in a diffusion environment) raises the possibility that large-scale in situ desalination of aquifers could be undertaken to support agriculture. ZVI desalination removes NaCl by an adsorption-desorption process in a multi-stage cross-coupled catalytic process. This study considers the potential application of two ZVI desalination catalyst types for in situ aquifer desalination. The feasibility of using ZVI catalysts when placed in situ within an aquifer to produce 100 m3 d-1 of partially desalinated water from a saline aquifer is considered.

  20. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement.

    Science.gov (United States)

    Suárez-Ojeda, María Eugenia; Kim, Jungkwon; Carrera, Julián; Metcalfe, Ian S; Font, Josep

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  1. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Ojeda, Maria Eugenia [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain); Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Kim, Jungkwon [Chemical Engineering and Analytical Sciences Department, University of Manchester, Manchester (United Kingdom); Carrera, Julian [Departament d' Enginyeria Quimica, Edifici Q-ETSE, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona, Catalonia (Spain); Metcalfe, Ian S. [Chemical Engineering and Advanced Materials Department, University of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom); Font, Josep [Departament d' Enginyeria Quimica, Escola Tecnica Superior d' Enginyeria Quimica, Universitat Rovira i Virgili, Av. Paisos Catalans 26, 43007 Tarragona, Catalonia (Spain)]. E-mail: jose.font@urv.cat

    2007-06-18

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P{sub O{sub 2}}) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P{sub O{sub 2}} were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P{sub O{sub 2}}, which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD{sub RB}) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.

  2. Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: Kinetics and biodegradability enhancement

    International Nuclear Information System (INIS)

    Suarez-Ojeda, Maria Eugenia; Kim, Jungkwon; Carrera, Julian; Metcalfe, Ian S.; Font, Josep

    2007-01-01

    Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15bar of oxygen partial pressure (P O 2 ) and at 180, 200 and 220deg. C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P O 2 were 140-160deg. C and 2-9bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160deg. C and 2 bar of P O 2 , which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD RB ) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture

  3. Bimetallic catalysts for continuous catalytic wet air oxidation of phenol.

    Science.gov (United States)

    Fortuny, A; Bengoa, C; Font, J; Fabregat, A

    1999-01-29

    Catalytic wet oxidation has proved to be effective at eliminating hazardous organic compounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2% of CoO, Fe2O3, MnO or ZnO with 10% CuO were supported on gamma-alumina by pore filling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at 140 degrees C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO-CuO, which was significantly higher than that obtained with the 10% CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.

  4. 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.

  5. Enhanced performance of solid oxide electrolysis cells by integration with a partial oxidation reactor: Energy and exergy analyses

    International Nuclear Information System (INIS)

    Visitdumrongkul, Nuttawut; Tippawan, Phanicha; Authayanun, Suthida; Assabumrungrat, Suttichai; Arpornwichanop, Amornchai

    2016-01-01

    Highlights: • Process design of solid oxide electrolyzer integrated with a partial oxidation reactor is studied. • Effect of key operating parameters of partial oxidation reactor on the electrolyzer performance is presented. • Exergy analysis of the electrolyzer process is performed. • Partial oxidation reactor can enhance the solid oxide electrolyzer performance. • Partial oxidation reactor in the process is the highest exergy destruction unit. - Abstract: Hydrogen production without carbon dioxide emission has received a large amount of attention recently. A solid oxide electrolysis cell (SOEC) can produce pure hydrogen and oxygen via a steam electrolysis reaction that does not emit greenhouse gases. Due to the high operating temperature of SOEC, an external heat source is required for operation, which also helps to improve SOEC performance and reduce operating electricity. The non-catalytic partial oxidation reaction (POX), which is a highly exothermic reaction, can be used as an external heat source and can be integrated with SOEC. Therefore, the aim of this work is to study the effect of operating parameters of non-catalytic POX (i.e., the oxygen to carbon ratio, operating temperature and pressure) on SOEC performance, including exergy analysis of the process. The study indicates that non-catalytic partial oxidation can enhance the hydrogen production rate and efficiency of the system. In terms of exergy analysis, the non-catalytic partial oxidation reactor is demonstrated to be the highest exergy destruction unit due to irreversible chemical reactions taking place, whereas SOEC is a low exergy destruction unit. This result indicates that the partial oxidation reactor should be improved and optimally designed to obtain a high energy and exergy system efficiency.

  6. 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.

  7. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm

    2000-01-01

    investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... between 0.1 and 0.3 V. There were no Faradaic reactions in the negative polarization region, and there was an anodic current which was less than 16% of the theoretical value for an exclusively Faradaic SO2 oxidation. Therefore the promotion effects at negative polarization are completely non-Faradaic. All...... the promotion effects have been explained as mainly due to charging of the electric double layer at the gold electrode. The effect at -0.2 V also depends on the V2O5 concentration and is more pronounced at higher V2O5 concentrations. This has been ascribed to a destruction of the vanadium polymeric chains...

  8. Catalytic conversion of methane: Carbon dioxide reforming and oxidative coupling

    KAUST Repository

    Takanabe, Kazuhiro

    2012-01-01

    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

  9. Catalytic/non-catalytic combination process for nitrogen oxides reduction

    International Nuclear Information System (INIS)

    Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

    1992-01-01

    This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

  10. Aerobic, catalytic oxidation of alcohols in ionic liquids

    Directory of Open Access Journals (Sweden)

    Souza Roberto F. de

    2006-01-01

    Full Text Available An efficient and simple catalytic system based on RuCl3 dissolved in ionic liquids has been developed for the oxidation of alcohols into aldehydes and ketones under mild conditions. A new fluorinated ionic liquid, 1-n-butyl-3-methylimidazolium pentadecafluorooctanoate, was synthesized and demonstrated better performance that the other ionic liquids employed. Moreover this catalytic system utilizes molecular oxygen as an oxidizing agent, producing water as the only by-product.

  11. 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....

  12. 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...

  13. 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

  14. Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon

    International Nuclear Information System (INIS)

    Rodriguez, Henry; Hoyos Bibian

    2004-01-01

    Electro-catalytic oxidation of ethanol on platinum-iridium mixtures supported on glassy carbon was studied, in acid media at different temperatures and concentrations. During the maturation time of deposited iridium, the surface is covered by an irreversible oxide formation, which affects the behavior of the catalytic mixture. The Pt 7 0 Ir 3 0 and Pt 9 0 Ir 1 0 mixtures seem to be a little more active than the Pt/C electrode at potentials below 800 mV (vs. HRE). In all electrodes appears two reactions: partial ethanol oxidation to produce acetaldehyde (main path of reaction at low temperatures and high electrode coverage with ethanol adsorption residues) and the total oxidation to carbon dioxide which is considerable at potential above 800 mV and it is increased with increasing temperature

  15. 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 surface...

  16. 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.

  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. Experimental and simulation analysis of hydrogen production by partial oxidation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Sikander, U. [National Univ. of Science and Technology, Islamabad (Pakistan)

    2014-10-15

    Partial oxidation of methanol is the only self-sustaining process for onboard production of hydrogen. For this a fixed bed catalytic reactor is designed, based on heterogeneous catalytic reaction. To develop an optimized process, simulation is carried out using ASPEN HYSYS v 7.1. Reaction kinetics is developed on the basis of Langmuir Hinshel wood model. 45:55:5 of CuO: ZnO: Al/sub 2/O/sub 3/ is used as a catalyst. Simulation results are studied in detail to understand the phenomenon of partial oxidation of methanol inside the reactor. An experimental rig is developed for hydrogen production through partial oxidation of methanol. Results obtained from process simulation and experimental work; are compared with each other. (author)

  19. Magnetic properties of partially oxidized Fe films

    Science.gov (United States)

    Garcia, Miguel Angel; Lopez-Dominguez, Victor; Hernando, Antonio

    Hybrid magnetic nanostructures exhibit appealing properties due to interface and proximity effects. A simple and interesting system of hybrid magnetic nanomaterials are partially oxidized ferromagnetic films. We have fabricated Fe films by thermal evaporation and performed a partial oxidation to magnetite (Fe3O4) by annealing in air at different times and temperatures. The magnetic properties of the films evolve from those of pure metallic iron to pure magnetite, showing intermediate states where the proximity effects control the magnetic behavior. At some stages, the magnetization curves obtained by SQUID and MOKE magnetometry exhibit important differences due to the dissimilar contribution of both phases to the magneto-optical response of the system This work has been supported by the Ministerio Español de Economia y Competitividad (MINECO) MAT2013-48009-C4-1. V.L.D and M.A.G. acknowledges financial support from BBVA foundation.

  20. 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.

  1. 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

  2. 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 ...

  3. 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...

  4. 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.

  5. 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.

  6. Rh promoted La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Palcheva, R., E-mail: radost@ic.bas.bg [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Olsbye, U.; Palcut, M. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway); Rauwel, P. [Department of Physics, SMN, University of Oslo, PO Box B 1048 Blindern, Oslo 0316 (Norway); Tyuliev, G.; Velinov, N. [Institute of Catalysis, Bulgarian Academy of Sciences, G. Bonchev Str., Bldg. 11, Sofia 1113 (Bulgaria); Fjellvåg, H.H. [InGAP Centre for Research-based Innovation, SMN, University of Oslo, PO Box 1033, Blindern, Oslo 0315 Norway (Norway)

    2015-12-01

    Graphical abstract: - Highlights: • Perovskites type-oxide La{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 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{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 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{sub 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{sub 2}, as confirmed by XRD. Data of MS identified Fe{sup 3+} ions in two distinctive coordination environments, and Fe{sup 4+} ions. The Rh{sub 2}O{sub 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{sub 2}, and surface carbon, CO{sub 2} and H{sub 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{sub 0.75}Sr{sub 0.25}(Fe{sub 0.8}Co{sub 0.2}){sub 1−x}Ga{sub x}O{sub 3-δ} perovskite materials.

  7. Catalytic production of metal carbonyls from metal oxides

    Science.gov (United States)

    Sapienza, Richard S.; Slegeir, William A.; Foran, Michael T.

    1984-01-01

    This invention relates to the formation of metal carbonyls from metal oxides and specially the formation of molybdenum carbonyl and iron carbonyl from their respective oxides. Copper is used here in admixed form or used in chemically combined form as copper molybdate. The copper/metal oxide combination or combined copper is utilized with a solvent, such as toluene and subjected to carbon monoxide pressure of 25 atmospheres or greater at about 150.degree.-260.degree. C. The reducing metal copper is employed in catalytic concentrations or combined concentrations as CuMoO.sub.4 and both hydrogen and water present serve as promoters. It has been found that the yields by this process have been salutary and that additionally the catalytic metal may be reused in the process to good effect.

  8. Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

    International Nuclear Information System (INIS)

    Sugunan, S.; Sherly, K.B.

    1994-01-01

    Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

  9. 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.)

  10. 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...... of the reaction conditions 4. Here, we therefore present an overview of the recent research about conversion of some lignin model compounds using heterogeneous catalysis in oxidation reactions....

  11. Catalytic dehydration of ethanol using transition metal oxide catalysts.

    Science.gov (United States)

    Zaki, T

    2005-04-15

    The aim of this work is to study catalytic ethanol dehydration using different prepared catalysts, which include Fe(2)O(3), Mn(2)O(3), and calcined physical mixtures of both ferric and manganese oxides with alumina and/or silica gel. The physicochemical properties of these catalysts were investigated via X-ray powder diffraction (XRD), acidity measurement, and nitrogen adsorption-desorption at -196 degrees C. The catalytic activities of such catalysts were tested through conversion of ethanol at 200-500 degrees C using a catalytic flow system operated under atmospheric pressure. The results obtained indicated that the dehydration reaction on the catalyst relies on surface acidity, whereas the ethylene production selectivity depends on the catalyst chemical constituents.

  12. 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.

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

    Science.gov (United States)

    Pozan, Gulin Selda

    2012-06-30

    The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. 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......-free conditions. Moreover, a detailed study on the performance and stability of the ruthenium hydroxide catalysts on magnesium-containing supports under reaction conditions was conducted. The aerobic oxidation of HMF to form another value-added chemical, 2,5-diformylfuran (DFF), was also investigated......Ox deposited on various metal oxides. Furthermore, this thesis presents the results of the catalytic aerobic oxidative degradation of higher alcohols over supported ruthenium hydroxide catalysts. A very efficient oxidative cleavage of vic-diols to form respective acids was also shown under examined conditions...

  15. Additive for vanadium and sulfur oxide capture in catalytic cracking

    International Nuclear Information System (INIS)

    Chin, A.A.; Sapre, A.V.; Sarli, M.S.

    1991-01-01

    This patent describes a fluid catalytic cracking process in which a hydrocarbon feedstock. It comprises: a vanadium contaminant in an amount of a least 2 ppmw is cracked under fluid catalytic cracking conditions with a solid, particulate cracking catalyst to produce cracking products of lower molecular weight while depositing carbonaceous material on the particles of cracking catalyst, separating the particles of cracking catalyst from the cracking products in the disengaging zone and oxidatively regenerating the cracking catalyst by burning off the deposited carbonaceous material in a regeneration zone, the improvement comprising reducing the make-up rate of the cracking catalyst by contacting the cracking feed with a particulate additive composition for passivating the vanadium content of the feed, comprising an alkaline earth metal oxide and an alkaline earth metal spinel

  16. Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas

    Institute of Scientific and Technical Information of China (English)

    魏永刚; 王华; 李孔斋

    2010-01-01

    The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...

  17. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  18. 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

  19. 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.

  20. 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.

  1. 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.

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  3. 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)

  4. 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.

  5. Catalytic activity trends of CO oxidation – A DFT study

    DEFF Research Database (Denmark)

    Jiang, Tao

    theoretical study of CO oxidation with experimental studies. The latter shows promoted catalytic activity when gold particle size decreases to 5 nm. Oxidizing CO by N2O was found to involve a CO␣O transition state, with atomic O adsorbed on the gold B5 sites and CO on the corners. On the other hand, CO...... and experiment were found to be the same. The experiment findings are in good agreement with our theoretical calculations. The second part of the thesis focuses on improving the convergence property of Quasi-Newton algorithm. The eigenvalues of the Hessian matrix of 54 atoms bulk Cu model are calculated......, and the sizes of eigenvalues follow power-law distribution. It is found that the anharmonicity of the weak modes lead to poor Newton step and poor Hessian update in BFGS type Quasi-Newton algorithm, which slow down the geometry optimization. Line search that fulfills Wolff conditions is then applied to improve...

  6. 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.

  7. Electrochemical and partial oxidation of methane

    Science.gov (United States)

    Singh, Rahul

    2008-10-01

    negligible coke formation on the novel fabricated anode by electroless plating process. Hydrogen is an environmentally cleaner source of energy. The recent increase in the demand of hydrogen as fuel for all types of fuel cells and petroleum refining process has boosted the need of production of hydrogen. Methane, a major component of natural gas is the major feedstock for production of hydrogen. The route of partial oxidation of methane to produce syngas (CO + H2) offers significant advantages over commercialized steam reforming process for higher efficiency and lower energy requirements. Partial oxidation of methane was studied by pulsing O2 into a CH4 flow over Rh/Al2O3 in a sequence of in situ infrared (IR) cell and fixed bed reactor at 773 K. The results obtained from the sequence of an IR cell followed by a fixed bed reactor show that (i) adsorbed CO produced possesses a long residence time, indicating that adsorbed oxygen leading to the formation of CO is significantly different from those leading to CO2 and (ii) CO2 is not an intermediate species for the formation of CO. In situ IR of pulse reaction coupled with alternating reactor sequence is an effective approach to study the primary and secondary reactions as well as the nature of their adsorbed species. As reported earlier, hydrogen remains to be the most effective fuel for fuel cells, the production of high purity hydrogen from naturally available resources such as coal, petroleum, and natural gas requires a number of energy-intensive steps, making fuel cell processes for stationary electric power generation prohibitively uneconomic. Direct use of coal or coal gas as the feed is a promising approach for low cost electricity generation. Coal gas solid oxide fuel cell was studied by pyrolyzing Ohio #5 coal to coal gas and transporting to a Cu anode solid oxide fuel cell to generate power. The study of coal-gas solid oxide fuel cell is divided into two sections, i.e., (i) understanding the composition of coal gas by

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

    Science.gov (United States)

    Dror, I.; Yecheskel, Y.; Berkowitz, B.

    2013-12-01

    Brominated flame retardants (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 which may lead to contamination of water resources. In this work we present the catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) in aqueous solution. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis are compared to Fenton oxidation and to reduction by nano zero-valent iron (nZVI). The two studied BFRs are shown to degrade fully by the nCuO system within hours to days. Shorter reaction times showed differences in reaction pathways and kinetics for the two compounds. 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 24 h, while the TBNPA was degraded by 85% within 12 hours. 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.

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

    Science.gov (United States)

    Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

    2017-01-01

    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 O3, 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 O3 catalytic decomposition and utilization. Benzene and O3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O3 was catalytically decomposed, generating highly reactive oxidants such as rad OH and rad O for benzene oxidation.

  10. 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.

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

    KAUST Repository

    Yin, S. M.; Duanmu, J. J.; Zhu, Yihan; Yuan, Y. F.; Guo, S. Y.; Yang, J. L.; Ren, Z. H.; Han, G. R.

    2017-01-01

    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.

  12. Effect of surface composition of yttrium-stabilized zirconia on partial oxidation of methane to synthesis gas.

    NARCIS (Netherlands)

    Zhu, J.J.; van Ommen, J.G.; Knoester, A.; Lefferts, Leonardus

    2005-01-01

    Catalytic partial oxidation of methane to synthesis gas (CPOM) over yttrium-stabilized zirconia (YSZ) was studied within a wide temperature window (500¿1100 °C). The catalysts were characterized by X-ray fluorescence (XRF) and low-energy ion scattering (LEIS). The influence of calcination

  13. 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

  14. The Mobility Enhancement of Indium Gallium Zinc Oxide Transistors via Low-temperature Crystallization using a Tantalum Catalytic Layer

    OpenAIRE

    Shin, Yeonwoo; Kim, Sang Tae; Kim, Kuntae; Kim, Mi Young; Oh, Saeroonter; Jeong, Jae Kyeong

    2017-01-01

    High-mobility indium gallium zinc oxide (IGZO) thin-film transistors (TFTs) are achieved through low-temperature crystallization enabled via a reaction with a transition metal catalytic layer. For conventional amorphous IGZO TFTs, the active layer crystallizes at thermal annealing temperatures of 600??C or higher, which is not suitable for displays using a glass substrate. The crystallization temperature is reduced when in contact with a Ta layer, where partial crystallization at the IGZO bac...

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

    Science.gov (United States)

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

    2012-06-30

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

  16. Cyclic catalytic upgrading of chemical species using metal oxide materials

    Science.gov (United States)

    White, James H; Schutte, Erick J; Rolfe, Sara L

    2013-05-07

    Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01Ba, Ca, La, or K; 0.02oxides.

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

    International Nuclear Information System (INIS)

    Huang, Haibao; Lu, Haoxian; Zhan, Yujie; Liu, Gaoyuan; Feng, Qiuyu; Huang, Huiling; Wu, Muyan; Ye, Xinguo

    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_3 catalytic oxidation. • O_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_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_3 catalytic decomposition and utilization. Benzene and O_3 removal efficiency reached as high as 97% and 100% after 360 min, respectively. O_3 was catalytically decomposed, generating highly reactive oxidants such as ·OH and ·O for benzene oxidation.

  18. 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.

  19. ESR study into mechanism of heterogeneous-catalytic oxidation on oxides

    Energy Technology Data Exchange (ETDEWEB)

    Topchieva, K V; Loginov, A Yu; Kostikov, S V [Moskovskij Gosudarstvennyj Univ. (USSR)

    1977-12-11

    The role of radical particles in heterogeneous-catalytic oxidation of H/sub 2/; CO; SO/sub 2/; NH/sub 3/; C/sub 3/H/sub 6/ on the rare earth oxides (yttrium, lanthanum, magnesium and scandium oxides) and alkaline earth metal oxides was studied by the ESR method. The conclusion was made about the great reactivity of the peroxide structures O/sub 2//sup -/ in the oxidation catalysis in comparison to other formulas of chemisorption oxigen on oxides. The kinetic investigations are chemisorption oxigen on oxides. The kinetic investigations are carried out on the change of the concentration of paramagnetic particles O/sub 2/ during the catalysis. On the basis of the received data the conclusion is made about the reaction process of catalytic oxidation on rare and alkaline-earth oxides according to radical-chain mechanism with the formation of radical particles O/sub 2//sup -/, CO/sub 3//sup -/, SO/sub 4//sup -/, CO/sub 2//sup -/ as interediate products.

  20. 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 ...

  1. Catalytic properties and biomedical applications of cerium oxide nanoparticles

    KAUST Repository

    Walkey, Carl D.; Das, Soumen C.; Seal, Sudipta; Erlichman, Joseph S.; Heckman, Karin L.; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William Thomas

    2014-01-01

    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?

  2. 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?

  3. Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

    Science.gov (United States)

    Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

    2018-05-01

    In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

  4. Catalytic oxidation of butyl acetate over silver-loaded zeolites

    International Nuclear Information System (INIS)

    Wong, Cheng Teng; Abdullah, Ahmad Zuhairi; Bhatia, Subhash

    2008-01-01

    The performance of silver-loaded zeolite (HY and HZSM-5) catalysts in the oxidation of butyl acetate as a model volatile organic compound (VOC) was studied. The objective was to find a catalyst with superior activity, selectivity towards deep oxidation product and stability. The catalyst activity was measured under excess oxygen condition in a packed bed reactor operated at gas hourly space velocity (GHSV) = 15,000-32,000 h -1 , reaction temperature between 150 and 500 deg. C and butyl acetate inlet concentration of 1000-4000 ppm. Both AgY and AgZSM-5 catalysts exhibited high activity in the oxidation of butyl acetate. Despite lower silver content, AgY showed better activity, attributed to better metal dispersion, surface characteristics and acidity, and its pore system. Total conversion of butyl acetate was achieved at above 400 deg. C. The oxidation of butyl acetate followed a simple power law model. The reaction orders, n and m were evaluated under differential mode by varying the VOC partial pressure between 0.004 and 0.018 atm and partial pressure of oxygen between 0.05 and 0.20 atm. The reaction rate was independent of oxygen concentration and single order with respect to VOC concentration. The activation energies were 19.78 kJ/mol for AgY and 32.26 kJ/mol for AgZSM-5, respectively

  5. Flame Synthesis of Composite Oxides for Catalytic Applications

    DEFF Research Database (Denmark)

    Jensen, Joakim Reimer

    2002-01-01

    gas (CO/CO2/H2) and an excellent thermal stability. Addition of alumina as a structural promoter is necessary in order to obtain a high activity for methanol formation. The binary systems, i.e., CuO/ZnO, ZnO/Al2O3 and CuO/Al2O3 are investigated as a prelude to the preparation of the ternary catalyst...... the flame temperature, the high temperature residence time and the precursor concentration. The Cu/ZnO/Al2O3 methanol catalyst is used as a model system for the preparation of catalytic materials. The flame synthesized catalyst exhibits a high and reproducible activity for methanol formation from synthesis...... 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...

  6. Catalytic decomposition of nitrogen dioxide over various metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Shimokawabe, M; Ohi, A; Takezawa, N [Dept. of Chemical Process Engineering, Hokkaido Univ., Sapporo (Japan)

    1992-06-30

    The catalytic decomposition of nitrogen oxide (NO2) was investigated over 18 metal oxides (Al2O3, SiO2, ZrO2, SnO2, TiO2, V2O5, Cr2O3, MnO2, Fe2O3, Co3O4, NiO, CuO, ZnO, MgO, CaO, La2O3, CeO2, and Nd2O3). The relationship between the specific rates of metal oxides (Me{sub x}O{sub y}) (Me{sub x}O{sub y-1} + 1/2O{sub 2} {yields} Me{sub x}O{sub y}) shows a V-shaped curve with a minimum at -{Delta}H around 700 kJ/mol. This suggests that the mechanism dealt with in this article switches at -{Delta}H = 700 kJ/mol. 1 fig., 1 tab., 20 refs.

  7. 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.

  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. Experimental Investigation of Flow Resistance in a Coal Mine Ventilation Air Methane Preheated Catalytic Oxidation Reactor

    Directory of Open Access Journals (Sweden)

    Bin Zheng

    2015-01-01

    Full Text Available This paper reports the results of experimental investigation of flow resistance in a coal mine ventilation air methane preheated catalytic oxidation reactor. The experimental system was installed at the Energy Research Institute of Shandong University of Technology. The system has been used to investigate the effects of flow rate (200 Nm3/h to 1000 Nm3/h and catalytic oxidation bed average temperature (20°C to 560°C within the preheated catalytic oxidation reactor. The pressure drop and resistance proportion of catalytic oxidation bed, the heat exchanger preheating section, and the heat exchanger flue gas section were measured. In addition, based on a large number of experimental data, the empirical equations of flow resistance are obtained by the least square method. It can also be used in deriving much needed data for preheated catalytic oxidation designs when employed in industry.

  10. 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

    2013-05-28

    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 Mn(3+)/Mn(4+) 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.

  11. 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....

  12. Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

    International Nuclear Information System (INIS)

    Hung, C.-M.

    2009-01-01

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H 2 PtCl 6 , Pd(NO 3 ) 3 and Rh(NO 3 ) 3 . Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h -1 in the wet catalytic processes

  13. Catalytic wet oxidation of ammonia solution: Activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hung, C.-M. [Department of Industry Engineering and Management, Yung-Ta Institute of Technology and Commerce, 316 Chung-shan Road, Linlo, Pingtung 909, Taiwan (China)], E-mail: hungcm1031@gmail.com

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H{sub 2}PtCl{sub 6}, Pd(NO{sub 3}){sub 3} and Rh(NO{sub 3}){sub 3}. Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h{sup -1} in the wet catalytic processes.

  14. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

  15. Conversion and Estrogenicity of 17β-estradiol During Photolytic/Photocatalytic Oxidation and Catalytic Wet-air Oxidation.

    Science.gov (United States)

    Bistan, Mirjana; Tišler, Tatjana; Pintar, Albin

    2012-06-01

    Estrogen 17β-estradiol (E2), produced by human body and excreted into municipal wastewaters, belongs to the group of endocrine disrupting compounds that are resistant to biological degradation. The aim of this study was to assess the efficiency of E2 removal from aqueous solutions by means of catalytic wet-air oxidation (CWAO) and photolytic/photocatalytic oxidation. CWAO experiments were conducted in a trickle-bed reactor at temperatures up to 230 °C and oxygen partial pressure of 10 bar over TiO2 and Ru/TiO2 solids. Photolytic/photocatalytic oxidation was carried out in a batch slurry reactor employing a TiO2 P-25 (Degussa) catalyst under visible or UV light. HPLC analysis and yeast estrogen screen assay were used to evaluate the removal of E2 and estrogenicity of treated samples. The latter was completely removed during photolytic/photocatalytic oxidation under UV (365 nm) light and photocatalytic oxidation under visible light. In CWAO experiments, complete removal of both E2 and estrogenicity from the feed solution were noticed in the presence of TiO2 and Ru/TiO2 catalysts.

  16. 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.

  17. Catalytic Oxidation of Toluene on Hydrothermally Prepared Ceria Nanocrystals

    Directory of Open Access Journals (Sweden)

    M. Duplančić

    2018-01-01

    Full Text Available Ceria nanocrystals were prepared hydrothermally and tested as potential catalysts for oxidation of volatile organic compounds using toluene as a model compound. Pure ceria with a crystallite size of 4 nm, determined by the Scherrer method from XRD pattern has been obtained. The specific surface area of the prepared nanoparticles determined by BET analysis yielded 201 m2 g–1, while the band gap of 3.2 eV was estimated from DRS spectrum via Tauc’s plot. Catalytic tests were performed on calcined ceria (500 °C with increased crystallite size (9 nm caused by thermal treatment. The tests showed good activities for the toluene oxidation with T50 temperatures, corresponding to 50 % toluene conversion, observed at 250 °C and even lower temperatures depending on the total flow rate of the gas mixture. The one-dimensional pseudo-homogeneous model of the fixed bed reactor was proposed to describe the reactor performance and the appropriate kinetic parameters were estimated. Good agreement between experimental data and the proposed model was observed.

  18. 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)

  19. 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

  20. 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)

  1. Cyanide Containing Wastewater Treatment by Ozone Enhanced Catalytic Oxidation over Diatomite Catalysts

    Directory of Open Access Journals (Sweden)

    Lin Mingguo

    2018-01-01

    Full Text Available Cyanide containing wastewater that discharged from gold mining process creates environmental problems due to the toxicity of cyanide. As one of the promising advanced oxidation process, catalytic oxidation with ozone is considered to be effective on the purification of cyanide. Diatomite, a natural mineral, was used as catalyst in this study. The effect of O3 dosage, salinity, initial cyanide concentration and initial pH condition were investigated. It was observed that the removal rate of cyanide was much higher in the catalytic oxidation with ozone process than the one in zone alone process. Alkaline condition was especially favorable for cyanide in catalytic oxidation with ozone. The ozone and catalytic oxidation with ozone were simulated by pseudo-first-order kinetics model. The apparent first-order rate constant contribution of the diatomite catalyst was 0.0757 min-1, and the contribution percentage was 65.77%.

  2. Selective catalytic oxidation of hydrocarbons as a challenge to the chemical engineer

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G [Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Inst. fuer Technische Chemie 1

    1977-11-01

    In the conversion of the most important chemical raw materials, natural oil and natural gas, to intermediate or end products, selective catalytic oxidation plays an increasing role. This method makes it possible in many cases to use more economical, single-step processes instead of the older multi-step processes. Using the typical example of propylene oxidation or ammonoxidation, the problems encountered by chemical engineers in the development of a heterogeneous-catalytic method of oxidation are demonstrated. The importance of systematic catalyst development is stressed. General aspects of the development of novel processes or the improvement of existing catalytic processes are discussed.

  3. Experimental Investigation of Flow Resistance in a Coal Mine Ventilation Air Methane Preheated Catalytic Oxidation Reactor

    OpenAIRE

    Zheng, Bin; Liu, Yongqi; Liu, Ruixiang; Meng, Jian; Mao, Mingming

    2015-01-01

    This paper reports the results of experimental investigation of flow resistance in a coal mine ventilation air methane preheated catalytic oxidation reactor. The experimental system was installed at the Energy Research Institute of Shandong University of Technology. The system has been used to investigate the effects of flow rate (200 Nm3/h to 1000 Nm3/h) and catalytic oxidation bed average temperature (20°C to 560°C) within the preheated catalytic oxidation reactor. The pressure drop and res...

  4. 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

  5. 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

  6. On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

    Science.gov (United States)

    Serra, José M.; Buchkremer, Hans-Peter

    Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

  7. 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.)

  8. 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...

  9. 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.

  10. 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.

  11. Catalytic reduction of nitric oxide with ammonia over transition metal ion-exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Sciyama, T; Arakawa, T; Matsuda, T; Yamazoe, N; Takita, Y

    1975-01-01

    The catalytic reduction of nitric oxide with ammonia was studied over transition metal ion-exchanged Y zeolite (Me-Y) catalysts. The reaction products are nitrogen, nitrous oxide, and water in all cases. Selectivities to N/sub 2/ are 60 to 80% on all the cation exchanged zeolite catalysts exhibiting a relatively minor variation with the cationic species exchanged. The copper (II)-Y catalyst exhibits low temperature activity and has an unusual catalytic activity-temperature profile with a maximum at 120/sup 0/C. The catalytic activity is enhanced considerably when a second cation, especially cobalt (II) or iron (III) is coexchanged together with Cu (II) in Y zeolite.

  12. Advances in the Partial Oxidation of Methane to Synthesis Gas

    Institute of Scientific and Technical Information of China (English)

    Quanli Zhu; Xutao Zhao; Youquan Deng

    2004-01-01

    The conversion and utilization of natural gas is of significant meaning to the national economy,even to the everyday life of people. However, it has not become a popular industrial process as expected due to the technical obstacles. In the past decades, much investigation into the conversion of methane,predominant component of natural gas, has been carried out. Among the possible routes of methane conversion, the partial oxidation of methane to synthesis gas is considered as an effective and economically feasible one. In this article, a brief review of recent studies on the mechanism of the partial oxidation of methane to synthesis gas together with catalyst development is wherein presented.

  13. 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

  14. 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.)

  15. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel

    Science.gov (United States)

    Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

    2016-01-01

    Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially ‘clean’ strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2•- radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO-) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems

  16. 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

    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...... 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...

  17. 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

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

    Science.gov (United States)

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

    2016-04-04

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

  19. 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

  20. 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)

  1. 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

  2. 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)

  3. Methane partial oxidation over a LaCr0.85Ru0.15O3 catalyst : Characterization, activity tests and kinetic modeling

    NARCIS (Netherlands)

    Melchiori, T.; Di Felice, L.; Mota, N.; Navarro, R.M.; Fierro, J.L.G.; Sint Annaland, van M.; Gallucci, F.

    2014-01-01

    A new LaCr0.85Ru0.15O3 perovskite-type catalyst for CH4 partial oxidation with a high activity and selectivity for syngas with good thermal stability and resistance against coking has been developed. In this paper, the catalyst preparation method, catalyst characterization, results of catalytic

  4. Selective catalytic oxidation of hydrocarbons as a challenge to the chemical engineer

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G [Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Lehrstuhl fuer Technische Chemie 1

    1978-08-01

    Selective catalytic oxidation is beginning to play a more and more significant role in the process of converting the most important chemical raw materials, crude oil and natural gas, into intermediate and end products. In many cases, this technique makes it possible to replace old processes consisting of many steps by more economical single-step reactions. The typical example of oxidation or ammoxidation of propylene demonstrates the problems which must be solved by the chemical engineer during the development of a heterogeneous catalytic oxidation process. The particular importance of a systematic development of a catalyst is emphasized. General aspects relating to the design of new catalytic processes, or the improvement of existing ones are also discussed.

  5. 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,...

  6. Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

    Science.gov (United States)

    Lashina, Elena A; Kaichev, Vasily V; Saraev, Andrey A; Vinokurov, Zakhar S; Chumakova, Nataliya A; Chumakov, Gennadii A; Bukhtiyarov, Valerii I

    2017-09-21

    The self-sustained kinetic oscillations in the oxidation of CH 4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO 2 , H 2 , and H 2 O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.

  7. Catalytic combustion of methane over mixed oxides derived from Co-Mg/Al ternary hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Zheng [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Jesus College, University of Oxford, OX1 3DW (United Kingdom); Yu, Junjie; Cheng, Jie; Hao, Zhengping [Research Centre of Eco-Environmental Sciences, CAS, Beijing 100085 (China); Xiao, Tiancun; Edwards, Peter P. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Jones, Martin O. [Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, OX1 3QR (United Kingdom); Rutherford Appleton Laboratory, Didcot, OX11 0QX (United Kingdom)

    2010-01-15

    Co{sub x}Mg{sub 3-x} /Al composite oxides (xCoMAO-800) were prepared by calcination of Co{sub x}Mg{sub 3-x}/Al hydrotalcites (x=0.0,0.5,1.0,1.5,2.0,2.5,3.0, respectively) at 800 C. The materials were characterized using XRD, TG-DSC, N{sub 2} adsorption-desorption and TPR. The methane catalytic combustion over the xCoMAO-800 was assessed in a fixed bed micro-reactor. The results revealed that cobalt can be homogenously dispersed into the matrices of the hydrotalcites and determines the structure, specific surface areas and porosity of the derived xCoMAO-800 oxide catalysts. The thermal stability and homogeneity of the hydrotalcites markedly depends on the cobalt concentration in the hydrotalcites. The Co-based hydrotalcite-derived oxides exhibit good activity in the catalytic combustion of methane. The catalytic activity over the xCoMAO-800 oxides enhances with increasing x up to 1.5, but subsequently decreases dramatically as cobalt loadings are further increased. The 1.5CoMAO-800 catalyst shows the best methane combustion activity, igniting methane at 450 C and completing methane combustion around 600 C. The catalytic combustion activity over the xCoMAO-800 oxides are closely related to the strong Co-Mg/Al interaction within the mixed oxides according to the TG-DSC, TPR and activity characteristics. (author)

  8. Low-temperature plasma-catalytic oxidation of formaldehyde in atmospheric pressure gas streams

    International Nuclear Information System (INIS)

    Ding Huixian; Zhu Aimin; Lu Fugong; Xu Yong; Zhang Jing; Yang Xuefeng

    2006-01-01

    Formaldehyde (HCHO) is a typical air pollutant capable of causing serious health disorders in human beings. This work reports plasma-catalytic oxidation of formaldehyde in gas streams via dielectric barrier discharges over Ag/CeO 2 pellets at atmospheric pressure and 70 0 C. With a feed gas mixture of 276 ppm HCHO, 21.0% O 2 , 1.0% H 2 O in N 2 , ∼99% of formaldehyde can be effectively destructed with an 86% oxidative conversion into CO 2 at GHSV of 16500 h -1 and input discharge energy density of 108 J l -1 . At the same experimental conditions, the conversion percentages of HCHO to CO 2 from pure plasma-induced oxidation (discharges over fused silica pellets) and from pure catalytic oxidation over Ag/CeO 2 (without discharges) are 6% and 33% only. The above results and the CO plasma-catalytic oxidation experiments imply that the plasma-generated short-lived gas phase radicals, such as O and HO 2 , play important roles in the catalytic redox circles of Ag/CeO 2 to oxidize HCHO and CO to CO 2

  9. Influence of ionizing radiation on the catalytic properties of oxide catalysts tested by hydrogen peroxide decomposition

    International Nuclear Information System (INIS)

    Mucka, V.

    1987-01-01

    Results of a study of some physical and catalytic properties of different oxide catalysts as affected by ionizing radiation (γ, n, e - ) and tested by the decomposition of hydrogen peroxide in aqueous solution are presented in this paper. The oxidation state of the active component present on the catalyst surface was found to be one of the most sensitive properties to the ionizing radiation. Changes of this state induced by γ-irradiation were found to be positive in most cases; electron pre-irradiation of the oxides leads, as a rule, to negative effects and the effects of neutron irradiation may be positive or negative. On the other hand, changes in the catalytic activity of the oxides after γ-or electron-irradiation seem to be mostly negative and positive, respectively; the effects of fast neutrons seem to vary here. Neither quantitative or qualitative correlation was found between the radiation-induced changes in these two quantities. The results give evidence that ionizing radiation principally affects the surface concentration of the catalytic sites. Both the character and magnitude of the changes in surface oxidation abilities and in catalytic activities of the oxide catalysts seem to be dependent upon the actual state of the catalyst surface. (author)

  10. 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 ...

  11. Catalytic properties of a titanium-antimony oxide system in oxidative ammonolysis of propylene

    Energy Technology Data Exchange (ETDEWEB)

    Zenkovets, G.A.; Tarasova, D.V.; Andrushkevich, T.V.; Aleshina, G.I.; Nikoro, T.A.; Ravilov, R.G.

    1979-03-01

    The catalytic properties of titanium-antimony oxide system in oxidative ammonolysis of propylene at 450/sup 0/C depended both on the catalyst and the reactant compositions. Stable and high (75-80Vertical Bar3<) selectivities for acrylonitrile and high activities were observed over catalysts containing 5-60 mole Vertical Bar3< Sb/sub 2/O/sub 4/ with 2Vertical Bar3< propylene and 3Vertical Bar3< ammonia in air at Vertical Bar3; 70Vertical Bar3< conversions. The selectivities of the catalysts for acetonitrile and acrolein did not exceed 5 and 1Vertical Bar3<, respectively. At high ammonia and propylene contents in the reaction mixture and over individual TiO/sub 2/ or Sb/sub 2/O/sub 4/ catalysts, the reaction selectivity shifted toward deep oxidation products. These findings were attributed to the reducing effect of propylene and ammonia at high concentrations on the active components of the catalyst, a solid solution of Sb in TiO/sub 2/ containing 5-7 mole Vertical Bar3< of Sb/sub 2/O/sub 4/ and a chemical compound with TiSb/sub 2/O/sub 6/ composition.

  12. A novel technique for hydrogen production from hog-manure in supercritical partial oxidation (SCWPO)

    Energy Technology Data Exchange (ETDEWEB)

    Youssef, Emhemmed A.; Charpentier, Paul [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Nakhla, George [Western Ontario Univ., London, ON (Canada). Dept. of Chemical and Biochemical Engineering; Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering; Elbeshbishy, Elsayed; Hafez, Hisham [Western Ontario Univ., London, ON (Canada). Dept. of Civil and Environmental Engineering

    2010-07-01

    In this study, the catalytic hydrogen production from hog manure using supercritical water partial oxidation was investigated in a batch reactor at a temperature of 500 C, and pressure of 28 MPa using several metallic catalysts. Hog manure was characterized by a total and soluble chemical oxygen demand (TCOD, SCOD) of 57000 and 28000 mg/L, total and volatile suspended solids (TSS, VSS) of 25000, 19000, and ammonia of 2400 mg/L, respectively. The order of H{sub 2} production was the following: Pd/AC > Ru/Al{sub 2}O{sub 3} > Ru/AC > AC > NaOH. The order of COD reduction efficiency was as follows: NaOH > Ru/AC > AC > Ru/Al{sub 2}O{sub 3} > Pd/AC. The behaviour of the volatile fatty acids (VFA's), ethanol, methanol, ammonia, H{sub 2}S, and Sulfate was investigated experimentally and discussed. A 35 % reduction in the H{sub 2} and CH{sub 4} yields was observed in the sequential gasification partial oxidation (oxidant at an 80 % of theoretical requirement) experiments compared to the gasification experiments (catalyst only). Moreover, this reduction in gas yields was coincided with a 45 % reduction in the liquid effluent chemical oxygen demand (COD), 60 % reduction of the ammonia concentration in the liquid effluent, and 20 % reduction in the H{sub 2}S concentration in the effluent gas. (orig.)

  13. 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)

  14. 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.

  15. Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

    Science.gov (United States)

    Zhang, Jing; Sun, Bo; Guan, Xiaohong; Wang, Hui; Bao, Hongliang; Huang, Yuying; Qiao, Junlian; Zhou, Gongming

    2013-11-19

    This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

  16. Effect of tungsten doping on catalytic properties of niobium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Franciane P.; Nogueira, Andre E. [Departamento de Quimica, Universidade Federal de Lavras, Lavras-MG (Brazil); Patricio, Patricia S.O., E-mail: patriciapatricio@cefetmg.br [Centro Federal de Educacao Tecnologica, CEFET, Belo Horizonte, MG (Brazil); Oliveira, Luiz C.A. [Departamento de Quimica, ICEx, Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil)

    2012-04-15

    A novel material based on niobia (Nb{sub 2}O{sub 5}) was synthesized to oxidize an organic compound in aqueous medium in the presence of H{sub 2}O{sub 2} after chemical modifications. Niobia was modified by doping with tungsten and also treating with H{sub 2}O{sub 2} in order to maximize the oxidative properties of this oxide. The analysis of the products from methylene blue dye oxidation with electro spray ionization mass spectrometry (ESI-MS) showed that the dye was successively oxidized to different intermediate compounds. The successive hydroxylation during this oxidation strongly suggests that highly reactive hydroxyl radicals are generated involving H{sub 2}O{sub 2} on the W-doped niobia grain surface. These results strongly suggest that the H{sub 2}O{sub 2} can regenerate in situ the peroxo group remaining active the system. (author)

  17. 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...

  18. Catalytic Oxidation of Mustard Simulants in Basic Solution

    National Research Council Canada - National Science Library

    Richardson, David

    2002-01-01

    .... Variation of bicarbonate source and the cosolvent can allow optimization of substrate solubility and oxidation rates for applications in chemical warfare agent decontamination, Use of surfactants...

  19. Catalytic wet air oxidation of aniline with nanocasted Mn-Ce-oxide catalyst.

    Science.gov (United States)

    Levi, R; Milman, M; Landau, M V; Brenner, A; Herskowitz, M

    2008-07-15

    The catalytic wet air oxidation of aqueous solution containing 1000 ppm aniline was conducted in a trickle-bed reactor packed with a novel nanocasted Mn-Ce-oxide catalyst (surface area of 300 m2/g) prepared using SBA-15 silica as a hard template. A range of liquid hourly space velocities (5-20 h(-1)) and temperatures (110-140 degrees C) at 10 bar of oxygen were tested. The experiments were conducted to provide the intrinsic performance of the catalysts. Complete aniline conversion, 90% TOC conversion, and 80% nitrogen mineralization were achieved at 140 degrees C and 5 h(-1). Blank experiments yielded relatively low homogeneous aniline (<35%) and negligible TOC conversions. Fast deactivation of the catalysts was experienced due to leaching caused by complexation with aniline. Acidification of the solution with HCI (molar HCI to aniline ratio of 1.2) was necessary to avoid colloidization and leaching of the nanoparticulate catalyst components. The catalyst displayed stable performance for over 200 h on stream.

  20. Catalytic oxidation of silicon by cesium ion bombardment

    International Nuclear Information System (INIS)

    Souzis, A.E.; Huang, H.; Carr, W.E.; Seidl, M.

    1991-01-01

    Results for room-temperature oxidation of silicon using cesium ion bombardment and low oxygen exposure are presented. Bombardment with cesium ions is shown to allow oxidation at O 2 pressures orders of magnitude smaller than with noble gas ion bombardment. Oxide layers of up to 30 A in thickness are grown with beam energies ranging from 20--2000 eV, O 2 pressures from 10 -9 to 10 -6 Torr, and total O 2 exposures of 10 0 to 10 4 L. Results are shown to be consistent with models indicating that initial oxidation of silicon is via dissociative chemisorption of O 2 , and that the low work function of the cesium- and oxygen-coated silicon plays the primary role in promoting the oxidation process

  1. 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.

  2. 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.

  3. 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

    (loose contact) the rate constants for a number of catalytic materials outline a volcano curve when plotted against their heats of oxygen chemisorption. However, the optima of the volcanoes correspond to different heats of chemisorption for the two contact situations. In both cases the activation...... 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...

  4. Basic approach to evaluate methane partial oxidation catalysts

    CSIR Research Space (South Africa)

    Parmaliana, A

    1993-09-01

    Full Text Available -phase reaction does not affect the catalytic pathways. Reasons for controversial results reported previously are discussed. They lie in the lack of an adequate experimental approach and in the generally adopted rule to evaluate the catalytic activity...

  5. 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…

  6. 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

  7. Interaction of dimethylamine with clean and partially oxidized copper surfaces

    Science.gov (United States)

    Kelber, J. A.; Rogers, J. W.; Banse, B. A.; Koel, B. E.

    1990-05-01

    The interaction of dimethylamine (DMA) with partially oxidized polycrystalline copper [Cu(poly)] and clean and partially oxidized Cu(110) between 110 and 500 K has been examined using electron stimulated desorption (ESD), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). ESD mass spectra of the DMA adsorbed on O/Cu(poly) between 112 and 230 K consistently display peaks at 44 amu [(CH 3) 2N] + and 46 amu [(CH 3) 2NH-H] +, but no significant parent peak at 45 amu [(CH 3) 2NH] +, even though this last feature is prominent in the gas-phase mass spectrum. OH - is not observed at temperatures below 184 K and the yield at higher temperatures is much less than that of O +. HREELS of DMA on clean and oxygen covered Cu(110) obtained at temperatures between 100 and 320 K show characteristic vibrational spectra for molecular DMA and no OH(a) vibrational modes. TPD results show that the desorption profiles of all the major peaks in the DMA mass spectrum follow that of the parent peak with no evidence for production of H 2O. The ESD, HREELS and TPD results all indicate that DMA is molecularly and reversibly adsorbed, with no significant formation of surface hydroxyl species. The results indicate that preferential adsorption of amines from amine/epoxy mixtures onto metal oxide surfaces could passivate the surface and prevent subsequent bonding to the epoxy resin.

  8. 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).

  9. 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

  10. SELECTIVE OXIDATION OF ALCOHOLS - COMPARING DIFFERENT CATALYTIC PROCESSES

    Science.gov (United States)

    Oxidation of alcohols to aldehydes, ketones or carboxylic acids is one of the most desirable chemical transformations in organic synthesis as these products are important precursors and intermediates for many drugs, vitamins and fragrances. Numerous methods are available for alc...

  11. 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.

  12. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    Science.gov (United States)

    González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

    2016-08-01

    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 H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) 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%V2O5) 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%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  13. Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    International Nuclear Information System (INIS)

    González, J.; Chen, L.F.; Wang, J.A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J.L.

    2016-01-01

    Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V 2 O 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 2 O 2 as oxidant. ODS activity was found to be proportional to the V 5+ /(V 4+ + V 5+ ) values of the catalysts, indicating that the surface vanadium pentoxide (V 2 O 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 2 O 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 2 O 5 /Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  14. Mixed oxides obtained from Co and Mn containing layered double hydroxides: Preparation, characterization, and catalytic properties

    International Nuclear Information System (INIS)

    Kovanda, Frantisek; Rojka, Tomas; Dobesova, Jana; Machovic, Vladimir; Bezdicka, Petr; Obalova, Lucie; Jiratova, Kveta; Grygar, Tomas

    2006-01-01

    Co-Mn-Al layered double hydroxides (LDHs) with various Co:Mn:Al molar ratios (4:2:0, 4:1.5:0.5, 4:1:1, 4:0.5:1.5, and 4:0:2) were prepared and characterized. Magnesium containing LDHs Co-Mg-Mn (2:2:2), Co-Mg-Mn-Al (2:2:1:1), and Co-Mg-Al (2:2:2) were also studied. Thermal decomposition of prepared LDHs and formation of related mixed oxides were studied using high-temperature X-ray powder diffraction and thermal analysis. The thermal decomposition of Mg-free LDHs starts by their partial dehydration accompanied by shrinkage of the lattice parameter c from ca. 0.76 to 0.66 nm. The dehydration temperature of the Co-Mn-Al LDHs decreases with increasing Mn content from 180 deg. C in Co-Al sample to 120 deg. C in sample with Co:Mn:Al molar ratio of 4:1.5:0.5. A subsequent step is a complete decomposition of the layered structure to nanocrystalline spinel, the complete dehydration, and finally decarbonation of the mixed oxide phase. Spinel-type oxides were the primary crystallization products. Mg-containing primary spinels had practically empty tetrahedral cationic sites. A dramatic increase of the spinel cell size upon heating and analysis by Raman spectroscopy revealed a segregation of Co-rich spinel in Co-Mn and Co-Mn-Al specimens. In calcination products obtained at 500 deg. C, the spinel mean coherence length was 5-10 nm, and the total content of the X-ray diffraction crystalline portion was 50-90%. These calcination products were tested as catalysts in the total oxidation of ethanol and decomposition of N 2 O. The catalytic activity in ethanol combustion was enhanced by increasing (Co+Mn) content while an optimum content of reducible components was necessary for high activity in N 2 O decomposition, where the highest conversions were found for calcined Co-Mn-Al sample with Co:Mn:Al molar ratio of 4:1:1

  15. Chemical polishing of partially oxidized T-111 alloy

    International Nuclear Information System (INIS)

    Teaney, P.E.

    1974-01-01

    The specimens were pressure-mounted in Bakelite and ground through 600 grit on silicon carbide papers. The specimens were rough-polished on a vibratory polisher for 4 to 6 h, using a water slurry of one micron alumina on Texmet, followed by 0.3-μ alumina on Texmet overnight. Final polishing was accomplished by continuous swabbing with a chemical polish. A chemical polish consisting of ten parts lactic acid, four parts nitric acid, and four parts hydrofluoric acid worked well for the T-111 parent material specimens; however, in the partially oxidized specimens, considerable pitting and staining occurred in the oxygen-affected zone and in the transition zone between the oxygen-affected zone and the parent material. A chemical polish was developed for the partially oxidized specimens by adjusting the ratio of the acids to ten parts lactic acid, two parts nitric acid, and two parts hydrofluoric acid. This slowed the chemical attack on the oxygen-affected zone considerably and, with continuous swabbing, the pitting and stain could be avoided. The specimens were rinsed and checked occasionally on the metallograph to determine when the proper polish had been obtained. Some specimens required intermittent polishing times up to 1 / 2 hour. No relationship could be established between the oxygen content of the specimen and the time required for chemical polishing in the partially oxidized specimens. However, the microstructure of the transition zone was the most difficult to obtain, and specimens with uniform reaction zones across the width of the specimen polished quicker than those with the transition zone

  16. 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.

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

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

    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.

  18. 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.

  19. 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)

  20. 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.)

  1. 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.)

  2. Oxidative Stress in Patients with Drug Resistant Partial Complex Seizure

    Directory of Open Access Journals (Sweden)

    Lourdes Lorigados Pedre

    2018-06-01

    Full Text Available Oxidative stress (OS has been implicated as a pathophysiological mechanism of drug-resistant epilepsy, but little is known about the relationship between OS markers and clinical parameters, such as the number of drugs, age onset of seizure and frequency of seizures per month. The current study’s aim was to evaluate several oxidative stress markers and antioxidants in 18 drug-resistant partial complex seizure (DRPCS patients compared to a control group (age and sex matched, and the results were related to clinical variables. We examined malondialdehyde (MDA, advanced oxidation protein products (AOPP, advanced glycation end products (AGEs, nitric oxide (NO, uric acid, superoxide dismutase (SOD, glutathione, vitamin C, 4-hydroxy-2-nonenal (4-HNE and nitrotyrosine (3-NT. All markers except 4-HNE and 3-NT were studied by spectrophotometry. The expressions of 4-HNE and 3-NT were evaluated by Western blot analysis. MDA levels in patients were significantly increased (p ≤ 0.0001 while AOPP levels were similar to the control group. AGEs, NO and uric acid concentrations were significantly decreased (p ≤ 0.004, p ≤ 0.005, p ≤ 0.0001, respectively. Expressions of 3-NT and 4-HNE were increased (p ≤ 0.005 similarly to SOD activity (p = 0.0001, whereas vitamin C was considerably diminished (p = 0.0001. Glutathione levels were similar to the control group. There was a positive correlation between NO and MDA with the number of drugs. The expression of 3-NT was positively related with the frequency of seizures per month. There was a negative relationship between MDA and age at onset of seizures, as well as vitamin C with seizure frequency/month. We detected an imbalance in the redox state in patients with DRCPS, supporting oxidative stress as a relevant mechanism in this pathology. Thus, it is apparent that some oxidant and antioxidant parameters are closely linked with clinical variables.

  3. 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.

  4. COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER; FINAL

    International Nuclear Information System (INIS)

    Phillip E. Savage

    1999-01-01

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, we examined the oxidation of phenol over a commercial catalyst and over bulk MnO(sub 2), bulk TiO(sub 2), and CuO supported on Al(sub 2) O(sub 3). We used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which we can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO(sub 2) yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that we could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, we performed experiments with bulk transition metal oxides. The bulk MnO(sub 2) and TiO(sub 2) catalysts enhance both the phenol disappearance and CO(sub 2) formation rates during SCWO. MnO(sub 2) does not affect the selectivity to CO(sub 2), or to the phenol dimers at a given phenol conversion. However, the selectivities to CO(sub 2) are increased and the selectivities to phenol dimers are decreased in the presence of TiO(sub 2) , which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of

  5. 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...

  6. 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

  7. 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.

  8. Catalytic oxidation of dichloromethane over sol-gel oxides supported Pd or Ni

    International Nuclear Information System (INIS)

    Martinez; Leidy Marcela; Montes, Consuelo

    2004-01-01

    Several supported Pd or Ni catalysts were synthesized by the sol-gel method using y-alumina, silica, sulfated zirconium and sulfated titanium as carriers. The resulting catalysts were characterized by XRD and nitrogen adsorption, and evaluated in the catalytic oxidation of dichloromethane. The effect of different parameters were determined, i.e. method of synthesis, temperature and the type of support. The durability of the best catalyst (0,5% Pd impregnated over sulfated titanium) was tested between 300 degrades Celsius and 350 degrades Celsius during 48 h. Under the conditions of this study, impregnated catalysts exhibited higher activity than those prepared by cogelation. Pd loaded catalysts showed higher conversion into CO 2 and HCl. Catalyst activity also increased with increasing temperature. Y-Alumina and sulfated titanium showed good activity but the formation of CO is favored instead of CO 2 . Therefore, bifunctional catalysts, i.e. containing metallic and acid sites appear to be required for the decomposition of methylene chloride into CO 2 and HCI

  9. Amine binding and oxidation at the catalytic site for photosynthetic water oxidation

    Science.gov (United States)

    Ouellette, Anthony J. A.; Anderson, Lorraine B.; Barry, Bridgette A.

    1998-01-01

    Photosynthetic water oxidation occurs at the Mn-containing catalytic site of photosystem II (PSII). By the use of 14C-labeled amines and SDS-denaturing PAGE, covalent adducts derived from primary amines and the PSII subunits, CP47, D2/D1, and the Mn-stabilizing protein, can be observed. When PSII contains the 18- and 24-kDa extrinsic proteins, which restrict access to the active site, no 14C labeling is obtained. NaCl, but not Na2SO4, competes with 14C labeling in Mn-containing PSII preparations, and the concentration dependence of this competition parallels the activation of oxygen evolution. Formation of 14C-labeled adducts is observed in the presence or in the absence of a functional manganese cluster. However, no significant Cl− effect on 14C labeling is observed in the absence of the Mn cluster. Isolation and quantitation of the 14C-labeled aldehyde product, produced from [14C]benzylamine, gives yields of 1.8 ± 0.3 mol/mol PSII and 2.9 ± 0.2 mol/mol in Mn-containing and Mn-depleted PSII, respectively. The corresponding specific activities are 0.40 ± 0.07 μmol(μmol PSII-hr)−1 and 0.64 ± 0.04 μmol(μmol PSII-hr)−1. Cl− suppresses the production of [14C]benzaldehyde in Mn-containing PSII, but does not suppress the production in Mn-depleted preparations. Control experiments show that these oxidation reactions do not involve the redox-active tyrosines, D and Z. Our results suggest the presence of one or more activated carbonyl groups in protein subunits that form the active site of PSII. PMID:9482863

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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)

  17. Catalytic Enhancement of Solid Carbon Oxidation in HDCFCs

    DEFF Research Database (Denmark)

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

    2014-01-01

    data as a function of temperature, anode and cathode atmospheres, and their flow rates are discussed. In the anode chamber, catalysts are mixed with the carbon-carbonate mixture. These catalysts include various manganese oxides (MnO2, Mn2O3, and Mn3O4, Fig. 1) and doped-ceria (CeO2, Ce1-xGdxO2, Ce1-x...

  18. 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.

  19. Modeling of termokinetic oscillations at partial oxidation of methane

    Science.gov (United States)

    Arutyunov, A. V.; Belyaev, A. A.; Inovenkov, I. N.; Nefedov, V. V.

    2017-12-01

    Partial oxidation of natural gas at moderate temperatures below 1500 K has significant interest for a number of industrial applications. But such processes can proceed at different unstable regimes including oscillating modes. Nonlinear phenomena at partial oxidation of methane were observed at different conditions. The investigation of the complex nonlinear system of equations that describes this process is a real method to insure its stability at industrial conditions and, at the same time, is an effective tool for its further enhancement. Numerical analysis of methane oxidation kinetics in the continuous stirred-tank reactor, with the use of detailed kinetic model has shown the possibility of the appearance of oscillating modes in the appropriate range of reaction parameters that characterize the composition, pressure, reagents flow, thermophysical features of the system, and geometry of the reactor. The appearance of oscillating modes is connected both with the reaction kinetics, heat release and sink and reagents introduction and removing. At that, oscillations appear only at a limited range of parameters, but can be accompanied by significant change in the yield of products. We have determined the range of initial temperature and pressure at which oscillations can be observed, if all other parameters remained fixed. The boundaries of existence of oscillations on the phase plane were calculated. It was shown that depending on the position inside the oscillation region the oscillations have different frequency and amplitude. It was reviled the role of heat exchange with the environment: at the absence of heat exchange the oscillating modes are impossible. In the vicinity of the boundary of phase range, where oscillations exist, significant change of concentration of some products were observed, for example, that of CO2, which in this case one of the principal products is. At that, insignificant increase in pressure not only change the character of CO2 behaving

  20. Preparation, characterization and catalytic activity of uranium-antimony oxide for selective oxidation of propene

    Energy Technology Data Exchange (ETDEWEB)

    Baussart, H.; Delobel, R.; Le Bras, M.; Le Maguer, D.; Leroy, J.M. (Ecole Nationale Superieure de Chimie de Lille, 59 (France). Lab. de Catalyse et Physico-Chimie des Solides)

    1982-02-01

    The selective oxidation of propene to acrolein over USb/sub 3/O/sub 10/ was studied in a continuous flow reactor. The experimental results show that the preparation of a well-defined catalyst of uniform composition depends on the temperature and time of calcination. The kinetic data indicate that acrolein is formed via a redox mechanism in which the surface of the catalyst is partially reduced. Moessbauer spectroscopy reveals the presence of Sb/sup 5 +/ and Sb/sup 3 +/ in the used catalyst. I.r. spectroscopy shows a structural modification. On the basis of these results it is concluded that each steady-state condition is characterized by a vacancy concentration leading to the observed modifications of the catalyst.

  1. 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.

  2. Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO4 under Oxygen Atmosphere

    International Nuclear Information System (INIS)

    Lee, Kang Hyeok; Ko, Kwang Youn

    2006-01-01

    KMnO 4 /alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O 2 atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO 4 /alumina reagent acts as a catalytic oxidant under O 2 atmosphere. Diphenyldiazomethane (Ph 2 CN 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

  3. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    Science.gov (United States)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

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

    Science.gov (United States)

    Tarabanko, Valery E.; Tarabanko, Nikolay

    2017-01-01

    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. PMID:29140301

  5. An empirical study on the preparation of the modified coke and its catalytic oxidation properties

    Science.gov (United States)

    Liu, Hao; Jiang, Wenqiang

    2017-05-01

    T As a methyl acrylic ester fungicide, pyraclostrobin has the advantages of high activity, wide sterilization spectrum and high safety level comparing with the traditional fungicide. Due to less toxicity and side effects on human and environment, the use of pyraclostrobin and its mixture in agriculture is increasing. The heavy use of pyraclostrobin will inevitably cause pollution to the biological and abiotic environment. Therefore, it is of great significance to do the research on the degradation of pyraclostrobin. In this study, coke, as matrix, was modified by chemical modification. The modified coke was used as the catalyst and the pyraclostrobin was used as the degradation object. The degradation experiment of pyraclostrobin was carried out by using catalytic oxidation. The catalytic oxidation performance of modified coke was studied. The result showed that in the catalytic oxidation system of using modified coke as catalyst and H2O2 as oxidant, the best reaction condition is as following: The modified coke which is modified by using 70% concentration nitric acid is used as catalyst; The dosage of the catalyst is10g; The dosage of H2O2 is 0.6ml; The reaction time is 6 hours.

  6. 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.

  7. 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.

  8. 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

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

    KAUST Repository

    Zhang, Tao; Li, Weiwei; Croue, Jean-Philippe

    2011-01-01

    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.

  10. 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.

  11. Partial oxidation process for producing a stream of hot purified gas

    Science.gov (United States)

    Leininger, T.F.; Robin, A.M.; Wolfenbarger, J.K.; Suggitt, R.M.

    1995-03-28

    A partial oxidation process is described for the production of a stream of hot clean gas substantially free from particulate matter, ammonia, alkali metal compounds, halides and sulfur-containing gas for use as synthesis gas, reducing gas, or fuel gas. A hydrocarbonaceous fuel comprising a solid carbonaceous fuel with or without liquid hydrocarbonaceous fuel or gaseous hydrocarbon fuel, wherein said hydrocarbonaceous fuel contains halides, alkali metal compounds, sulfur, nitrogen and inorganic ash containing components, is reacted in a gasifier by partial oxidation to produce a hot raw gas stream comprising H{sub 2}, CO, CO{sub 2}, H{sub 2}O, CH{sub 4}, NH{sub 3}, HCl, HF, H{sub 2}S, COS, N{sub 2}, Ar, particulate matter, vapor phase alkali metal compounds, and molten slag. The hot raw gas stream from the gasifier is split into two streams which are separately deslagged, cleaned and recombined. Ammonia in the gas mixture is catalytically disproportionated into N{sub 2} and H{sub 2}. The ammonia-free gas stream is then cooled and halides in the gas stream are reacted with a supplementary alkali metal compound to remove HCl and HF. Alkali metal halides, vaporized alkali metal compounds and residual fine particulate matter are removed from the gas stream by further cooling and filtering. The sulfur-containing gases in the process gas stream are then reacted at high temperature with a regenerable sulfur-reactive mixed metal oxide sulfur sorbent material to produce a sulfided sorbent material which is then separated from the hot clean purified gas stream having a temperature of at least 1000 F. 1 figure.

  12. Simultaneous sorption and catalytic oxidation of trivalent antimony by Canna indica derived biochars.

    Science.gov (United States)

    Cui, Xiaoqiang; Ni, Qijun; Lin, Qiang; Khan, Kiran Yasmin; Li, Tingqiang; Khan, Muhammad Bilal; He, Zhenli; Yang, Xiaoe

    2017-10-01

    The simultaneous sorption and oxidation of Sb(III) on biochars were investigated using batch experiments. The biochars were derived from Canna indica at different pyrolysis temperatures (300-600 °C, referred as CIB300-CIB600), and characterized by FTIR, BET, XRD, SEM-EDS, EPR and Boehm titration. The Sb(III) sorption data could be well fitted by both the Langmuir and Freundlich models, and the pseudo-second order model is best for describing the kinetic data. The maximum Sb(III) sorption capacity of CIB300 was 16.1 mg g -1 , which was greater than that of other biochars. Inner-sphere complexation with oxygen-containing functional groups and coordination with π electrons are the possible sorption mechanisms. It is worthwhile to note that 4.7-32.3% of Sb(III) was oxidized to Sb(V) after sorption equilibration, demonstrating the occurrence of Sb(III) oxidation during the sorption process. Further study of oxidation under anoxic condition confirmed the catalytic role of biochar for Sb(III) oxidation, and free radicals in biochars were crucial for electron transfer. CIB400 exhibited the highest catalytic oxidative ability for Sb(III), which could be ascribe to its reserve of more electroactive polyphenolic macromolecule and less electroinactive cellulose. These results imply that biochars have good potential as a green effective sorbent for remediation of Sb(III) contaminated water, and simultaneously reduce the toxicity of Sb(III) by catalytic oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Shape-dependent plasma-catalytic activity of ZnO nanomaterials coated on porous ceramic membrane for oxidation of butane.

    Science.gov (United States)

    Sanjeeva Gandhi, M; Mok, Young Sun

    2014-12-01

    In order to explore the effects of the shape of ZnO nanomaterials on the plasma-catalytic decomposition of butane and the distribution of byproducts, three types of ZnO nanomaterials (nanoparticles (NPs), nanorods (NRs) and nanowires (NWs)) were prepared and coated on multi-channel porous alumina ceramic membrane. The structures and morphologies of the nanomaterials were confirmed by X-ray diffraction method and scanning electron microscopy. The observed catalytic activity of ZnO in the oxidative decomposition of butane was strongly shape-dependent. It was found that the ZnO NWs exhibited higher catalytic activity than the other nanomaterials and could completely oxidize butane into carbon oxides (COx). When using the bare or ZnO NPs-coated ceramic membrane, several unwanted partial oxidation and decomposition products like acetaldehyde, acetylene, methane and propane were identified during the decomposition of butane. When the ZnO NWs- or ZnO NRs-coated membrane was used, however, the formation of such unwanted byproducts except methane was completely avoided, and full conversion into COx was achieved. Better carbon balance and COx selectivity were obtained with the ZnO NWs and NRs than with the NPs. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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 MnO x , CoO x . 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 CO 2 selectivity is observed in presence of the corona and catalysts, as compared to those with the plasma alone. The results show that MnO x and CoO x catalysts can dissociate the in-plasma produced ozone to oxygen radicals, which enhances the TCE decomposition. (author)

  15. 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.

  16. Catalytic Oxidation of Soot on a Novel Active Ca-Co Dually-Doped Lanthanum Tin Pyrochlore Oxide

    Directory of Open Access Journals (Sweden)

    Lijie Ai

    2018-04-01

    Full Text Available A novel active Ca-Co dually-doping pyrochlore oxide La2−xCaxSn2−yCoyO7 catalyst was synthesized by the sol-gel method for catalytic oxidation of soot particulates. The microstructure, atomic valence, reduction, and adsorption performance were investigated by X-ray powder diffraction (XRD, scanning electron microscope (SEM, Fourier-transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, H2-TPR (temperature-programmed reduction, and in situ diffuse reflection infrared Fourier transformed (DRIFTS techniques. Temperature programmed oxidation (TPO tests were performed with the mixture of soot-catalyst under tight contact conditions to evaluate the catalytic activity for soot combustion. Synergetic effect between Ca and Co improved the structure and redox properties of the solids, increased the surface oxygen vacancies, and provided a suitable electropositivity for oxide, directly resulting in the decreased ignition temperature for catalyzed soot oxidation as low as 317 °C. The presence of NO in O2 further promoted soot oxidation over the catalysts with the ignition temperature decreased to about 300 °C. The DRIFTS results reveal that decomposition of less stable surface nitrites may account for NO2 formation in the ignition period of soot combustion, which thus participate in the auxiliary combustion process.

  17. 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)

  18. [Kinetics of catalytic wet air oxidation of phenol in trickle bed reactor].

    Science.gov (United States)

    Li, Guang-ming; Zhao, Jian-fu; Wang, Hua; Zhao, Xiu-hua; Zhou, Yang-yuan

    2004-05-01

    By using a trickle bed reactor which was designed by the authors, the catalytic wet air oxidation reaction of phenol on CuO/gamma-Al2O3 catalyst was studied. The results showed that in mild operation conditions (at temperature of 180 degrees C, pressure of 3 MPa, liquid feed rate of 1.668 L x h(-1) and oxygen feed rate of 160 L x h(-1)), the removal of phenol can be over 90%. The curve of phenol conversion is similar to "S" like autocatalytic reaction, and is accordance with chain reaction of free radical. The kinetic model of pseudo homogenous reactor fits the catalytic wet air oxidation reaction of phenol. The effects of initial concentration of phenol, liquid feed rate and temperature for reaction also were investigated.

  19. 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...

  20. 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.

  1. 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.

  2. Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

    Science.gov (United States)

    Brown, Elizabeth S; Robinson, Jerome R; McCoy, Aaron M; McGaff, Robert W

    2011-06-14

    We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

  3. 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.

  4. Production of reduction gases: partial oxidation of hydrocarbons and coal

    Energy Technology Data Exchange (ETDEWEB)

    Tippmer, K

    1976-04-01

    After some general remarks on reduction gas and quality demands, the Texaco process of partial oxidation with scrubbing is dealt with. A comparison of current iron-sponge techniques shows that a heat demand below 3 M kcal/t Fe should be envisaged, which means that heavy fuel oil or coal should be used. The special features of oxygen generation, coal processing, demands made on fuel oil, gasoline, and natural gas, gas generation, soot recovery, hydrogen sulphide-carbon dioxide scrubbing, system Benfield HP process, recycle-carbon dioxide scrubbing, auxiliary steam system, gas preheating, recycle gas cooling and compression, process data and heat balances for natural gas (one-heat system) and heating fuel oil or naphtha (two-heat system) are given.

  5. The Mobility Enhancement of Indium Gallium Zinc Oxide Transistors via Low-temperature Crystallization using a Tantalum Catalytic Layer.

    Science.gov (United States)

    Shin, Yeonwoo; Kim, Sang Tae; Kim, Kuntae; Kim, Mi Young; Oh, Saeroonter; Jeong, Jae Kyeong

    2017-09-07

    High-mobility indium gallium zinc oxide (IGZO) thin-film transistors (TFTs) are achieved through low-temperature crystallization enabled via a reaction with a transition metal catalytic layer. For conventional amorphous IGZO TFTs, the active layer crystallizes at thermal annealing temperatures of 600 °C or higher, which is not suitable for displays using a glass substrate. The crystallization temperature is reduced when in contact with a Ta layer, where partial crystallization at the IGZO back-channel occurs with annealing at 300 °C, while complete crystallization of the active layer occurs at 400 °C. The field-effect mobility is significantly boosted to 54.0 cm 2 /V·s for the IGZO device with a metal-induced polycrystalline channel formed at 300 °C compared to 18.1 cm 2 /V·s for an amorphous IGZO TFT without a catalytic layer. This work proposes a facile and effective route to enhance device performance by crystallizing the IGZO layer with standard annealing temperatures, without the introduction of expensive laser irradiation processes.

  6. 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

  7. The chemical and catalytic properties of nanocrystalline metal oxides prepared through modified sol-gel synthesis

    Science.gov (United States)

    Carnes, Corrie Leigh

    The goal of this research was to synthesize, characterize and study the chemical properties of nanocrystalline metal oxides. Nanocrystalline (NC) ZnO, CuO, NiO, Al2O3, and the binary Al2O 3/MgO and ZnO/CuO were prepared through modified sol gel methods. These NC metal oxides were studied in comparison to the commercial (CM) metal oxides. The samples were characterized by XRD, TGA, FTIR, BET, and TEM. The NC samples were all accompanied by a significant increase in surface area and decrease in crystallite size. Several chemical reactions were studied to compare the NC samples to the CM samples. One of the reactions involved a high temperature reaction between carbon tetrachloride and the oxide to form carbon dioxide and the corresponding metal chloride. A similar high temperature reaction was conducted between the metal oxide and hydrogen sulfide to form water and the corresponding metal sulfide. A room temperature gas phase adsorption was studied where SO2 was adsorbed onto the oxide. A liquid phase adsorption conducted at room temperature was the destructive adsorption of paraoxon (a toxic insecticide). In all reactions the NC samples exhibited greater activity, destroying or adsorbing a larger amount of the toxins compared to the CM samples. To better study surface area effects catalytic reactions were also studied. The catalysis of methanol was studied over the nanocrystalline ZnO, CuO, NiO, and ZnO/CuO samples in comparison to their commercial counterparts. In most cases the NC samples proved to be more active catalysts, having higher percent conversions and turnover numbers. A second catalytic reaction was also studied, this reaction was investigated to look at the support effects. The catalysis of cyclopropane to propane was studied over Pt and Co catalysts. These catalysts were supported onto NC and CM alumina by impregnation. By observing differences in the catalytic behavior, support effects have become apparent.

  8. 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

  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-...

  10. Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

    Science.gov (United States)

    Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

    2014-02-01

    Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

  11. 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

  12. Catalytic ozonation of fenofibric acid over alumina-supported manganese oxide

    Energy Technology Data Exchange (ETDEWEB)

    Rosal, Roberto, E-mail: roberto.rosal@uah.es [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain); Gonzalo, Maria S.; Rodriguez, Antonio; Garcia-Calvo, Eloy [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain)

    2010-11-15

    The catalytic ozonation of fenofibric acid was studied using activated alumina and alumina-supported manganese oxide in a semicontinuous reactor. The rate constants at 20 deg. C for the non-catalytic reaction of fenofibric acid with ozone and hydroxyl radicals were 3.43 {+-} 0.20 M{sup -1} s{sup -1} and (6.55 {+-} 0.33) x 10{sup 9} M{sup -1} s{sup -1}, respectively. The kinetic constant for the catalytic reaction between fenofibric acid and hydroxyl radicals did not differ significantly from that of homogeneous ozonation, either using Al{sub 2}O{sub 3} or MnO{sub x}/Al{sub 2}O{sub 3}. The results showed a considerable increase in the generation of hydroxyl radicals due to the use of catalysts even in the case of catalytic runs performed using a real wastewater matrix. Both catalysts promoted the decomposition of ozone in homogeneous phase, but the higher production of hydroxyl radicals corresponded to the catalyst with more activity in terms of ozone decomposition. We did not find evidence of the catalysts having any effect on rate constants, which suggests that the reaction may not involve the adsorption of organics on catalyst surface.

  13. 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.

  14. 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.

  15. Magnetic bimetallic nanoparticles supported reduced graphene oxide nanocomposite: Fabrication, characterization and catalytic capability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lei; Wu, Tao; Xu, Xiaoyang; Xia, Fengling; Na, Heya [School of Science, Tianjin University, Tianjin 300072 (China); Liu, Yu, E-mail: liuyuls@163.com [School of Science, Tianjin University, Tianjin 300072 (China); Qiu, Haixia [School of Science, Tianjin University, Tianjin 300072 (China); Wang, Wei [School of Chemical Engineering, Tianjin University, Tianjin 300072 (China); Gao, Jianping, E-mail: jianpinggao2012@126.com [School of Science, Tianjin University, Tianjin 300072 (China)

    2015-04-15

    Highlights: • Ni and Ag nanoparticles loaded on RGO (Ni–Ag@RGO) were fabricated in a one-pot reaction. • The Ni–Ag@RGO were excellent catalysts for the reduction of 4-nitrophenol. • The Ni–Ag@RGO showed superior catalytic activity for photodegradation of methyl orange. • The Ni–Ag@RGO exhibit good reusability in a magnetic field. - Abstract: A facile method for preparing Ni–Ag bimetallic nanoparticles supported on reduced graphene oxide (Ni–Ag@RGO hybrid) has been established. Hydrazine hydrate was used as the reducing agent to reduce the graphene oxide, Ni{sup 2+} and Ag{sup +} to form Ni–Ag@RGO hybrid. The prepared hybrid was further characterized by X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscopy. Interestingly, the prepared material shown good magnetic properties, which were determined by vibrating sample magnetometer. In addition, the Ni–Ag@RGO hybrid exhibited excellent catalytic activity for the reduction of 4-nitrophenol and the photodegradation of methyl orange. The catalytic process was monitored by determining the change in the concentration of the reactants with time using ultraviolet–visible absorption spectroscopy. After completion of the reaction, the catalyst can be separated from the reaction system simply under a magnet field and shows good recyclability.

  16. Reduced graphene oxide supported platinum nanocubes composites: one-pot hydrothermal synthesis and enhanced catalytic activity

    International Nuclear Information System (INIS)

    Li, Fumin; Gao, Xueqing; Xue, Qi; Li, Shuni; Chen, Yu; Lee, Jong-Min

    2015-01-01

    Reduced graphene oxide (rGO) supported platinum nanocubes (Pt-NCs) composites (Pt-NCs/rGO) were synthesized successfully by a water-based co-chemical reduction method, in which polyallylamine hydrochloride acted as a multi-functional molecule for the functionalization of graphene oxide, anchorage of Pt II precursor, and control of Pt crystal facets. The morphology, structure, composition, and catalytic property of Pt-NCs/rGO composites were characterized in detail by various spectroscopic techniques. Transmission electron microscopy images showed well-defined Pt-NCs with an average size of 9 nm uniformly distributed on the rGO surface. The as-prepared Pt-NCs/rGO composites had excellent colloidal stability in the aqueous solution, and exhibited superior catalytic activity towards the hydrogenation reduction of nitro groups compared to commercial Pt black. The improved catalytic activity originated from the abundant exposed Pt{100} facets of Pt-NCs, excellent dispersion of Pt-NCs on the rGO surface, and synergistic effect between Pt-NCs and rGO. (paper)

  17. Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst

    International Nuclear Information System (INIS)

    Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R.; Picasso Escobar, Gino I.

    2013-01-01

    The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C 12 H 15 N 3 O 2 S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 o C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H 2 NCONH 2 ·H 2 O 2 ) as oxidizing agent and methanol (CH 3 OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N 2 (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (author)

  18. 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

  19. Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene

    Energy Technology Data Exchange (ETDEWEB)

    Cantatore, Valentina, E-mail: valcan@chalmers.se; Panas, Itai [Department of Chemistry and Chemical Engineering, Energy & Materials, Chalmers University of Technology, Gothenburg (Sweden)

    2016-04-21

    We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing boron doped graphene. The present study is based on the observation that boron doped graphene and O—N=N—O{sup −} act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N—O dissociation. Two N{sub 2} + O{sub 2} product channels, one of which favoring N{sub 2}O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N{sub 2} + O{sub 2} formation pathways are contrasted by a side reaction that brings to N{sub 3}O{sub 3}{sup −} formation and decomposition into N{sub 2}O + NO{sub 2}{sup −}.

  20. Modelling of catalytic oxidation of NH3 and reduction of NO on limestone during sulphur capture

    DEFF Research Database (Denmark)

    Kiil, Søren; Bhatia, Suresh K.; Dam-Johansen, Kim

    1996-01-01

    activity with respect to each species involved. An existing particle model, the Grain-Micrograin Model, which simulates sulphur capture on limestone under oxidizing conditions is considered in the modelling. Simulation results in good qualitative agreement with experimental data are obtained here......A theoretical study of the complex transient system of simultaneous sulphur capture and catalytic reactions of N-containing compounds taking place on a single limestone particle is conducted. The numerical technique developed previously by the authors (Kiil et al. 1994) based on collocation...... for the catalytic chemistry of NH3 during simultaneous sulphur capture on a Stevns Chalk particle. The reduction of NO by NH3 over CaSO4 (which is the product of the reaction between SO2, O2 and limestone) was found to be important because this reaction could explain the change in selectivity with increased solid...

  1. 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.)

  2. Effect of phase interaction on catalytic CO oxidation over the SnO_2/Al_2O_3 model catalyst

    International Nuclear Information System (INIS)

    Chai, Shujing; Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang; Xian, Hui; Mi, Wenbo; Li, Xingang

    2017-01-01

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"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_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_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"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_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  3. 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

  4. 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.

  5. Metallo-deuteroporphyrin as a biomimetic catalyst for the catalytic oxidation of lignin to aromatics.

    Science.gov (United States)

    Zhu, Chenjie; Ding, Weiwei; Shen, Tao; Tang, Chenglun; Sun, Chenguo; Xu, Shichao; Chen, Yong; Wu, Jinglan; Ying, Hanjie

    2015-05-22

    A series of metallo-deuteroporphyrins derived from hemin were prepared as models of the cytochrome P450 enzyme. With the aid of the highly active Co(II) deuteroporphyrin complex, the catalytic oxidation system was applied for the oxidation of several lignin model compounds, and high yields of monomeric products were obtained under mild reaction conditions. It was found that the modified cobalt deuteroporphyrin that has no substituents at the meso sites but does have the disulfide linkage in the propionate side chains at the β sites exhibited much higher activity and stability than the synthetic tetraphenylporphyrin. The changes in the propionate side chains can divert the reactivity of cobalt deuteroporphyrins from the typical CC bond cleavage to CO bond cleavage. Furthermore, this novel oxidative system can convert enzymolysis lignin into depolymerized products including a significant portion of well-defined aromatic monomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A catalytic wet oxidation process for mixed waste volume reduction/recycling

    International Nuclear Information System (INIS)

    Dhooge, Patrick M.

    1992-01-01

    Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

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

    International Nuclear Information System (INIS)

    Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej

    2016-01-01

    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

  8. 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

  9. Catalytic nanoporous membranes

    Science.gov (United States)

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

    2013-08-27

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

  10. Catalytic Role of Manganese Oxides in Prebiotic Nucleobases Synthesis from Formamide.

    Science.gov (United States)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2016-06-01

    Origin of life processes might have begun with the formation of important biomonomers, such as amino acids and nucleotides, from simple molecules present in the prebiotic environment and their subsequent condensation to biopolymers. While studying the prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide, the manganese oxides demonstrated not only good binding for formamide but demonstrated novel catalytic activity. A novel one pot manganese oxide catalyzed synthesis of pyrimidine nucleobases like thymine is reported along with the formation of other nucleobases like purine, 9-(hydroxyacetyl) purine, cytosine, 4(3 H)-pyrimidinone and adenine in acceptable amounts. The work reported is significant in the sense that the synthesis of thymine has exhibited difficulties especially under one pot conditions and also such has been reported only under the catalytic activity of TiO2. The lower oxides of manganese were reported to show higher potential as catalysts and their existence were favored by the reducing atmospheric conditions prevalent on early Earth; thereby confirming the hypothesis that mineral having metals in reduced form might have been more active during the course of chemical evolution. Our results further confirm the role of formamide as a probable precursor for the formation of purine and pyrimidine bases during the course of chemical evolution and origin of life.

  11. In situ synthesis and catalytic application of reduced graphene oxide supported cobalt nanowires

    Science.gov (United States)

    Xu, Zhiqiang; Long, Qin; Deng, Yi; Liao, Li

    2018-05-01

    Controlled synthesis of magnetic nanocomposite with outstanding catalytic performances is a promising strategy in catalyst industry. We proposed a novel concept for fabrication of reduced graphene oxide-supported cobalt nanowires (RGO/Co-NWs) nanocomposite as high-efficient magnetic catalyst. Unlike the majority of experiments necessitating harsh synthesis conditions such as high-pressure, high-temperature and expensive template, here the RGO/Co-NWs were successfully prepared in aqueous solution under mild conditions with the assistance of external magnetic field. The synthetic process was facile and external magnetic force was adopted to induce the unidirectional self-assembly of cobalt crystals on graphene oxide to form RGO/Co-NWs. The possible formation mechanism laid on the fact that the dipole magnetic moments of the nanoparticles were aligned along the magnetic induction lines with the external magnetic field direction resulting in the formation of nanowires elongating in the direction of the magnetization axis. Simultaneously, a series of controlled reactions were conducted to illuminate the effect of graphene oxide, external magnetic field and PVP on the morphology and size of RGO/Co-NWs in the present approach. More importantly, the nanocomposite exhibited a high catalytic performance towards ammonia borane. Hence the novel nanocomposite holds a great potential for technological applications such as catalyst industry.

  12. 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

    The electrochemical behavior of the molten V2O5-M2S2O7 (M = K, Cs, or Na) system was studied using a gold working electrode at 440 degrees C in argon and air atmosphere. The aim of the present investigation was to find a possible correlation between the promoting effect of Cs+ and Na+ ions...... 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...

  13. 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

  14. 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

  15. 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

  16. 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.

  17. Selective oxidations in microstructured catalytic reactions - A review and an overview of own work on fuel processing for fuel cells

    NARCIS (Netherlands)

    Hessel, V.; Kolb, G.A.; Cominos, V.; Loewe, H.; Nikolaidis, G.; Zapf, R.; Ziogas, A.; Schouten, J.C.; Delsman, E.R.; Croon, de M.H.J.M.; Santamaria, J.; Iglesia, de la O.; Mallada, R.

    2006-01-01

    This review is concerned about catalytic gas-phase oxidation reactions in microreactors, typically being performed in wall-coated microchannels. Not included are liquid and gas-liquid oxidations which are typically done in reactor designs different from the ones considered here. The first part of

  18. Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

    Energy Technology Data Exchange (ETDEWEB)

    Constance L. Senior [Reaction Engineering International, Salt Lake City, UT (United States)

    2006-01-15

    A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420{sup o}C, with space velocities varying from 1900 to 5000 hr{sup -1}. Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. 20 refs., 9 figs., 2 tabs.

  19. Rare earth oxide aero- and xerogels. Tuning porosity and catalytic properties

    International Nuclear Information System (INIS)

    Neumann, Bjoern

    2013-11-01

    Heterogeneous catalysts to this day are still largely developed on the basis of trial and error. This is due to the great difficulty of creating custom-designed structures at the nanometer scale using traditional preparation methods. In the course of recent rapid developments in the material sciences, however, it has become possible to create materials with custom-designed properties from the macroscopic down into the nanometer range. The purpose of the present study was to make use of this potential for catalysis. The task was to modify the porosity and composition of selected rare earth oxides that promise well as catalysts with the goal of obtaining good results in terms of oxidative reactions and oxidative coupling. One major focus was on chemical sol-gel methods and in particular on what is referred to as the epoxide addition method. Extensive work was put into the characterisation and catalytic testing of aerogels and xerogels of pure rare earth oxides as well as of hybrid systems of rare earth oxides and aluminium oxide. Furthermore, thin xerogel films and macroporous monoliths were produced, the latter using a direct foaming method. The results of this work confirm the high potential of sol-gel chemistry for making porous materials of variable and controllable porosity and composition available for heterogeneous catalysis and creating more powerful catalysts. [de

  20. 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.

  1. CATALYTIC OXIDATION OF ALCOHOLS AND EPOXIDATION OF OLEFINS WITH HYDROGEN PEROXIDE AS OXIDANT

    Science.gov (United States)

    Hydrogen peroxide (H2O2) is an ideal oxidant of choice for these oxidations due to economic and environmental reasons by giving water as a by-product. Two catalysts used are vanadium phosphorus oxide (VPO) and Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a...

  2. 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.

  3. 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.

  4. Preparation of carbon nanotube-neodymium oxide composite and research on its catalytic performance

    International Nuclear Information System (INIS)

    Zhao Lei; Wang Zhihua; Han Dongmei; Tao Dongliang; Guo Guangsheng

    2009-01-01

    Carbon Nanotube-Neodymium Oxide (CNT-Nd 2 O 3 ) composite was prepared by using acid treated carbon nanotubes (CNTs) and neodymium nitrate in the presence of sodium dodecyl sulfate and ammonia liquid. Techniques of transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and differential thermal analysis (DTA) are used to characterize the morphology, structure, composition and catalytic property of the CNT-Nd 2 O 3 composite. The experimental results show that the Nd 2 O 3 nanoparticles, which have an average diameter of about 30-40 nm, are loaded on the surface of carbon nanotube. Compared with pure Nd 2 O 3 nanorods, the CNT-Nd 2 O 3 composite can catalyze the thermal decomposition of ammonium perchlorate more effectively. The sampling methods of the experimental samples made a difference on the catalytic experiment results, and the best catalytic result was obtained when de-ionized water served as the solvent of ammonium perchlorate

  5. Synthesis, characterization, and catalytic application of ordered mesoporous carbon–niobium oxide composites

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Juan-Li; Gao, Shuang; Liu, Chun-Ling; Liu, Zhao-Tie; Dong, Wen-Sheng, E-mail: wsdong@snnu.edu.cn

    2014-11-15

    Graphical abstract: The ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process. - Highlights: • Ordered mesoporous carbon–niobium oxide composites were synthesized. • The content of Nb{sub 2}O{sub 5} in the composites could be tuned from 38 to 75%. • Niobium species were highly dispersed in amorphous carbon framework walls. • The composites exhibited good catalytic performance in the dehydration of fructose. - Abstract: Ordered mesoporous carbon–niobium oxide composites have been synthesized by a multi-component co-assembly method associated with a carbonization process using phenolic resol as carbon source, niobium chloride as precursor and amphiphilic triblock copolymer Pluronic F127 as template. The resulting materials were characterized using a combination of techniques including differential scanning calorimetry–thermogravimetric analysis, N{sub 2} physical adsorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show that with increasing the content of Nb{sub 2}O{sub 5} from 38 to 75% the specific surface area decreases from 306.4 to 124.5 m{sup 2} g{sup −1}, while the ordered mesoporous structure is remained. Niobium species is well dispersed in the amorphous carbon framework. The mesoporous carbon–niobium oxide composites exhibit high catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural. A 100% conversion of fructose and a 76.5% selectivity of 5-hydroxymethylfurfural were obtained over the carbon–niobium oxide composite containing 75% Nb{sub 2}O{sub 5} under the investigated reaction conditions.

  6. Catalytic incineration of CO and VOC emissions over supported metal oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, Per-Olof

    1999-05-01

    Catalytic incineration is one of the methods to reduce the emissions of CO and VOCs. Low operation temperature and low catalyst cost are essential parameters for catalytic incinerators. Pt/Al{sub 2}O{sub 3} catalysts are frequently used today, but the cheaper metal oxide catalysts can be very competitive if comparable overall activity is obtained. This thesis concerns how it is possible to decrease the operation temperature for supported metal oxide catalysts by using different supports, active metal oxides and additives. In the thesis it is demonstrated that different copper oxide based catalysts have the best activity and durability for complete oxidation among several tested metal oxide catalysts. CuO{sub x} supported on TiO{sub 2} and Al{sub 2}O{sub 3} showed increased activity with the CuO{sub x} loading up to the threshold coverage for formation of crystalline CuO particles, which is 12 {mu}mol/m{sup 2} on TiO{sub 2} and 6 {mu}mol/m{sup 2} on Al{sub 2}O{sub 3}. Up to the threshold coverage for CuO formation, well dispersed copper oxide species were formed on TiO{sub 2}, and a dispersed copper aluminate surface phase was formed on Al{sub 2}O{sub 3}. Durability tests showed accelerated sintering of TiO{sub 2} by copper, but stabilisation was possible by modification of the TiO{sub 2} with CeO{sub x} before the deposition of CuO{sub x}. The stabilisation was obtained by formation of a Ce-O-Ti surface phase. Addition of CeO{sub x} also enhanced the activity of the copper oxide species thanks to favourable interaction between the active copper oxide species and the CeO{sub x} on the support, which could be seen as increased reducibility in TPR experiments. The increased activity and reducibility was also observed for CuO{sub x} supported on ceria modified Al{sub 2}O{sub 3}. In this regard it was shown that CuO{sub x} deposited on CeO{sub 2}(001) surfaces was substantially more active for CO oxidation than copper oxide deposited on CeO{sub 2}(111) Surfaces. This

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Room-temperature synthesis and enhanced catalytic performance of silver-reduced graphene oxide nanohybrids

    International Nuclear Information System (INIS)

    Thu, Tran Viet; Ko, Pil Ju; Phuc, Nguyen Huu Huy; Sandhu, Adarsh

    2013-01-01

    The synthesis of supported, ultrasmall metallic nanoparticles (NPs) is of great importance for catalytic applications. In this study, silver-reduced graphene oxide nanohybrids (Ag–rGO NHs) were prepared by reducing Ag ions and graphene oxide (GO) at room temperature using sodium borohydride (NaBH 4 ) and trisodium citrate. The resulting products were characterized using UV–Vis spectroscopy, X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy. The rich chemistry of GO surface provided many sites for the nucleation of Ag ions and efficiently limited their growth. Ag NPs were uniformly grown on basal planes of rGO with a high density (∼1,700 NPs μm −2 ) and well-defined size (3.6 ± 0.6 nm) as evidenced in SEM and HRTEM studies. The resulting Ag–rGO NHs were readily dispersed in water and exhibited enhanced catalytic activity toward the reduction of 4-nitrophenol by NaBH 4 in comparison to unsupported Ag NPs. The role of rGO as an excellent support for Ag catalyst is discussed

  12. Room-temperature synthesis and enhanced catalytic performance of silver-reduced graphene oxide nanohybrids

    Energy Technology Data Exchange (ETDEWEB)

    Thu, Tran Viet, E-mail: thu@eiiris.tut.ac.jp; Ko, Pil Ju, E-mail: ko@eiiris.tut.ac.jp [Toyohashi University of Technology, Electronics-Inspired Interdisciplinary Research Institute (Japan); Phuc, Nguyen Huu Huy [Toyohashi University of Technology, Department of Electrical and Electronic Information Engineering (Japan); Sandhu, Adarsh [Toyohashi University of Technology, Electronics-Inspired Interdisciplinary Research Institute (Japan)

    2013-10-15

    The synthesis of supported, ultrasmall metallic nanoparticles (NPs) is of great importance for catalytic applications. In this study, silver-reduced graphene oxide nanohybrids (Ag-rGO NHs) were prepared by reducing Ag ions and graphene oxide (GO) at room temperature using sodium borohydride (NaBH{sub 4}) and trisodium citrate. The resulting products were characterized using UV-Vis spectroscopy, X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy. The rich chemistry of GO surface provided many sites for the nucleation of Ag ions and efficiently limited their growth. Ag NPs were uniformly grown on basal planes of rGO with a high density ({approx}1,700 NPs {mu}m{sup -2}) and well-defined size (3.6 {+-} 0.6 nm) as evidenced in SEM and HRTEM studies. The resulting Ag-rGO NHs were readily dispersed in water and exhibited enhanced catalytic activity toward the reduction of 4-nitrophenol by NaBH{sub 4} in comparison to unsupported Ag NPs. The role of rGO as an excellent support for Ag catalyst is discussed.

  13. 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

    Heterogeneous catalysis studies were conducted on two crushed solid oxide fuel cell (SOFC) anodes in fixed-bed reactors. The baseline anode was Ni/ScYSZ (Ni/scandia and yttria stabilized zirconia), the other was Ni/ScYSZ modified with Pd/doped ceria (Ni/ScYSZ/Pd-CGO). Three main types......-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...

  14. Partial oxidation of dimethyl ether using the structured catalyst Rh/Al2O3/Al prepared through the anodic oxidation of aluminum.

    Science.gov (United States)

    Yu, B Y; Lee, K H; Kim, K; Byun, D J; Ha, H P; Byun, J Y

    2011-07-01

    The partial oxidation of dimethyl ether (DME) was investigated using the structured catalyst Rh/Al2O3/Al. The porous Al2O3 layer was synthesized on the aluminum plate through anodic oxidation in an oxalic-acid solution. It was observed that about 20 nm nanopores were well developed in the Al2O3 layer. The thickness of Al2O3 layer can be adjusted by controlling the anodizing time and current density. After pore-widening and hot-water treatment, the Al2O3/Al plate was calcined at 500 degrees C for 3 h. The obtained delta-Al2O3 had a specific surface area of 160 m2/g, making it fit to be used as a catalyst support. A microchannel reactor was designed and fabricated to evaluate the catalytic activity of Rh/Al2O3/Al in the partial oxidation of DME. The structured catalyst showed an 86% maximum hydrogen yield at 450 degrees C. On the other hand, the maximum syngas yield by a pack-bed-type catalyst could be attained by using a more than fivefold Rh amount compared to that used in the structured Rh/Al2O3/Al catalyst.

  15. Detection of Intracellular Reduced (Catalytically Active) SHP-1 and Analyses of Catalytically Inactive SHP-1 after Oxidation by Pervanadate or H2O2.

    Science.gov (United States)

    Choi, Seeyoung; Love, Paul E

    2018-01-05

    Oxidative inactivation of cysteine-dependent Protein Tyrosine Phosphatases (PTPs) by cellular reactive oxygen species (ROS) plays a critical role in regulating signal transduction in multiple cell types. The phosphatase activity of most PTPs depends upon a 'signature' cysteine residue within the catalytic domain that is maintained in the de-protonated state at physiological pH rendering it susceptible to ROS-mediated oxidation. Direct and indirect techniques for detection of PTP oxidation have been developed (Karisch and Neel, 2013). To detect catalytically active PTPs, cell lysates are treated with iodoacetyl-polyethylene glycol-biotin (IAP-biotin), which irreversibly binds to reduced (S - ) cysteine thiols. Irreversible oxidation of SHP-1 after treatment of cells with pervanadate or H 2 O 2 is detected with antibodies specific for the sulfonic acid (SO 3 H) form of the conserved active site cysteine of PTPs. In this protocol, we describe a method for the detection of the reduced (S - ; active) or irreversibly oxidized (SO 3 H; inactive) form of the hematopoietic PTP SHP-1 in thymocytes, although this method is applicable to any cysteine-dependent PTP in any cell type.

  16. 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

  17. Influence of thermal treatments on the basic and catalytic properties of Mg,Al-mixed oxides derived from hydrotalcites

    Directory of Open Access Journals (Sweden)

    Bastiani R.

    2004-01-01

    Full Text Available This work studied the influence of calcination conditions on basic properties and catalytic performance of Mg,Al-mixed oxides derived from a hydrotalcite sample (Al/(Al+Mg=0.20. Various heating rates, calcination atmospheres and lengths of calcination at 723K were evaluated. TPD of CO2 and retroaldolization of diacetone alcohol (DAA were used to determine the basic properties of the mixed oxides. The basic site density determined by TPD of CO2 showed a better correlation with catalytic activity for acetone/citral aldol condensation than the relative basicity obtained from retroaldolization of DAA. Calcination atmosphere was the parameter that influenced most the basic and the catalytic properties of the Mg,Al-mixed oxides, with calcination under dry air being the best choice.

  18. A study of the homogeneous stages in the catalytic oxidation of naphthalene, o-xylene, and benzene over a vibratory-fluidized catalyst bed

    Energy Technology Data Exchange (ETDEWEB)

    Korneichuk, G P; Stasevich, V P; Shaprinskaya, T M; Girushtin, G G; Gritsenko, V I; Zelenchukova, T G

    1978-01-01

    To identify the conditions for minimizing homogeneous states, the reaction kinetics were studied in a vibrating gradientless quartz reactor both in the presence and absence of the catalyst. A tenfold decrease of the reactional space in the absence of catalyst inhibited the oxidation (e.g., from a 68% conversion to 10% at 500/sup 0/C for o-xylene, and from 100% to 2% at 580/sup 0/C for benzene), whereas increasing the surface-volume ratio of the reactor increased the oxidation rate for benzene, which indicated that noncatalytic oxidation follows a radical-chain mechanism and involves both homogeneous (mainly) and heterogeneous stages. Catalytic oxidation carried out in a small volume (to avoid the homogeneous states) followed a heterogeneous mechanism up to 580/sup 0/C for naphthalene and o-xylene, and up to 550/sup 0/C for benzene. At higher temperatures, however, volume oxidation of benzene to carbon oxides was detected, which was favored by intense reactor vibration (i.e., increasing free space between catalyst grains), constituted 27% at 564/sup 0/C and 40% at 584/sup 0/C, and probably followed a heterogeneous-homogeneous mechanism. The partial oxidation products (i.e., phthalic and (for benzene) maleic anhydride) formed entirely by a heterogeneous mechanism. Tables and graphs.

  19. 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)

  20. 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)

  1. 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.

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

    Science.gov (United States)

    Ganini, Douglas; Leinisch, Fabian; Kumar, Ashutosh; Jiang, JinJie; Tokar, Erik J; Malone, Christine C; Petrovich, Robert M; Mason, Ronald P

    2017-08-01

    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 (H 2 O 2 ) per molecule of chromophore [5,6]. Even though it has been proposed that this process is non-catalytic and generates nontoxic levels of H 2 O 2 [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 (O 2 •- ) and H 2 O 2 in the presence of NADH. Generation of the free radical O 2 •- and H 2 O 2 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. Published by Elsevier B.V.

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

    Science.gov (United States)

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

    2016-09-01

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

  4. 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.

  5. Partial oxidation of methane in a temperature-controlled dielectric barrier discharge reactor

    KAUST Repository

    Zhang, Xuming; Cha, Min

    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

  6. 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

  7. 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.

  8. Gold Decorated Graphene for Rapid Dye Reduction and Efficient Electro Catalytic Oxidation of Ethanol

    Science.gov (United States)

    Siddhardha, R. S.; Kumar v, Lakshman; Kaniyoor, A.; Podila, R.; Kumar, V. S.; Venkataramaniah, K.; Ramaprabhu, S.; Rao, A.; Ramamurthy, S. S.; Clemson University Team; Sri Sathya Sai Institute of Higher Learning Team; IITMadras Team

    2013-03-01

    A well known disadvantage in fabrication of metal-graphene composite is the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. Here, we demonstrate a novel one pot synthesis of gold nanoparticles (AuNPs) by laser ablation of gold strip and simultaneous decoration of these on functionalized graphene derivatives. Not only the impregnation of AuNPs was linker free, but also the synthesis by itself was surfactant free. This resulted in in-situ decoration of pristine AuNPs on functionalized graphene derivatives. These materials were well characterized and tested for catalytic applications pertaining to dye reduction and electrooxidation. The catalytic reduction rates are 1.4 x 102 and 9.4x102 times faster for Rhodamine B and Methylene Blue dyes respectively, compared to earlier reports. The enhanced rate involves synergistic interplay of electronic relay between AuNPs and the dye, also charge transfer between the graphene system and dye. In addition, the onset potential for ethanol oxidation was found to be more negative ~ 100 mV, an indication of its promising application in direct ethanol fuel cells.

  9. 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)

  10. 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.

  11. 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.

  12. 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...

  13. 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.

  14. 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.

  15. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Zhou, Yong [Eco-materials and Renewable Energy Research Center (ERERC), School of Physics, National Lab of Solid State Microstructure, ERERC, Nanjing University, Nanjing 210093 (China); Pei, Chonghua, E-mail: peichonghua@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China)

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  16. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    International Nuclear Information System (INIS)

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua

    2014-01-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS 13 C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g

  17. Annihilation characteristics of positrons in oxide powders in relation to catalytic activities

    International Nuclear Information System (INIS)

    Ito, K.; Ohtsu, Y.; Tanigawa, S.; Enomura, A.; Tsuda, N.

    1982-01-01

    The annihilation chaaracteristics in magnesium oxide powders were studied by the measurements of Doppler broadening of annihilation radiations. MgO powders are well known as a solid base and are utilized as a catalyst for the reactions which start by extracting protons from molecules such as decomposition of alcohol. The isochronal annealing behavior of annihilation characteristics in the process Mg(OH) 2 → MgO was found to correspond just to the change in the number of basic points, specific surface area and catalytic activities in some reactions. From the results of the thermal equilibrium measurements of MgO powders after dehydration, the temperature dependence of S parameter can be considered as the thermal activation process of the escape of positrons from trapped states at surface to form positroniums. The derived value of this activation energy was 0.187 eV. (Auth.)

  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.

    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

  19. 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

  20. Catalytic activity of bimetal-containing Co,Pd systems in the oxidation of carbon monoxide

    Science.gov (United States)

    Oleksenko, L. P.; Lutsenko, L. V.

    2013-02-01

    The catalytic activity of low-percentage Co,Pd systems on ZSM-5, ERI, SiO2, and Al2O3 supports in the oxidation of CO was studied. The activity of bimetal-containing catalysts was shown to depend on the nature of the catalyst and the amount and ratio of their active components. According to the results of thermoprogrammed reduction with H2 (H2 TPR) and X-ray photoelectron spectroscopy (XPS) data, the metals are distributed as isolated cations or Coδ+-O-Pdδ+ clusters with cobalt and palladium cations surrounded by off-lattice oxygen in Co,Pd systems. The 0.8% Co,0.5% Pd-ZSM-5 bimetal catalysts were found to be more active due to the presence of clusters.

  1. On the Pt(+) and Rh(+) Catalytic Activity in the Nitrous Oxide Reduction by Carbon Monoxide.

    Science.gov (United States)

    Rondinelli, F; Russo, N; Toscano, M

    2008-11-11

    Nitrous oxide activation by CO in the presence of platinum and rhodium monocations was elucidated by density functional methods for ground and first excited states. Platinum and rhodium cations fulfill the thermodynamic request for the oxygen-atom transport that allows the catalytic cycle to be completed, but actually, just the first one meaningfully improves the kinetics of the process. For both catalysts, the reaction pathways show the only activation barrier in correspondence of nitrogen release and monoxide cation formation. The kinetic analysis of the potential energy profile, in agreement with ICP/SIFT MS experimental data, indicates that platinum performs more in the reduction, while the whole process is not sufficiently fast in the case of rhodium ionic catalyst.

  2. A novel [Bmim]PW/HMS catalyst with high catalytic performance for the oxidative desulfurization process

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Ling; Luo, Guangqing; Kang, Lihua; Zhu, Mingyuan; Dai, Bin [Shihezi University, Shihezi (China)

    2013-02-15

    To effectively reduce the sulfur content in model fuel, [Bmim]PW/HMS catalyst was synthesized through impregnating the hexagonal mesoporous silica (HMS) support by phosphotungstic acid (HPW) and ionic liquid [Bmim] HSO{sub 4}. Physical structure characterizations of the catalysts showed that HMS retained mesoporous structure, and [Bmim] PW was well dispersed on the support of HMS. The catalytic activity of the [Bmim]PW/HMS was evaluated in the oxidative desulfurization process, and the optimal reaction conditions including loading of the catalysts, reaction temperature, catalyst amount, O/S (H{sub 2}O{sub 2}/sulfur) molar ratio and agitation speed were investigated. Under the optimal reaction conditions, the conversion of benzothiophene (BT), dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) could reach 79%, 98%, 88%, respectively.

  3. A novel [Bmim]PW/HMS catalyst with high catalytic performance for the oxidative desulfurization process

    International Nuclear Information System (INIS)

    Tang, Ling; Luo, Guangqing; Kang, Lihua; Zhu, Mingyuan; Dai, Bin

    2013-01-01

    To effectively reduce the sulfur content in model fuel, [Bmim]PW/HMS catalyst was synthesized through impregnating the hexagonal mesoporous silica (HMS) support by phosphotungstic acid (HPW) and ionic liquid [Bmim] HSO 4 . Physical structure characterizations of the catalysts showed that HMS retained mesoporous structure, and [Bmim] PW was well dispersed on the support of HMS. The catalytic activity of the [Bmim]PW/HMS was evaluated in the oxidative desulfurization process, and the optimal reaction conditions including loading of the catalysts, reaction temperature, catalyst amount, O/S (H 2 O 2 /sulfur) molar ratio and agitation speed were investigated. Under the optimal reaction conditions, the conversion of benzothiophene (BT), dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) could reach 79%, 98%, 88%, respectively

  4. Synthesis of Nitrogen-Doped Mesoporous Carbon for the Catalytic Oxidation of Ethylbenzene

    Science.gov (United States)

    Wang, Ruicong; Yu, Yifeng; Zhang, Yue; Lv, Haijun; Chen, Aibing

    2017-06-01

    Nitrogen-doped ordered mesoporous carbon (NOMC) was fabricated via a simple hard-template method by functionalized ionic liquids as carbon and nitrogen source, SBA-15 as a hard-template. The obtained NOMC materials have a high nitrogen content of 5.55 %, a high surface area of 446.2 m2 g-1, and an excellent performance in catalysing oxidation of ethylbenzene. The conversion rate of ethylbenzene can be up to 84.5% and the yield of acetophenone can be up to 69.9%, the results indicated that the NOMC materials have a faster catalytic rate and a higher production of acetophenone than catalyst-free and CMK-3, due to their uniform pore size, high surface area and rich active sites in the carbon pore walls.

  5. 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.

  6. 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.

  7. 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

  8. 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)

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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 −3 s −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 app ), 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. Selective catalytic oxidation: a new catalytic approach to the desulfurization of natural gas and liquid petroleum gas for fuel cell reformer applications

    Science.gov (United States)

    Lampert, J.

    In both natural gas and liquid petroleum gas (LPG), sulfur degrades the performance of the catalysts used in fuel reformers and fuel cells. In order to improve system performance, the sulfur must be removed to concentrations of less than 200 ppbv (in many applications to less than 20 ppbv) before the fuel reforming operation. Engelhard Corporation presents a unique approach to the desulfurization of natural gas and LPG. This new method catalytically converts the organic and inorganic sulfur species to sulfur oxides. The sulfur oxides are then adsorbed on a high capacity adsorbent. The sulfur compounds in the fuel are converted to sulfur oxides by combining the fuel with a small amount of air. The mixture is then heated from 250 to 270 °C, and contacted with a monolith supported sulfur tolerant catalyst at atmospheric pressure. When Engelhard Corporation demonstrated this catalytic approach in the laboratory, the result showed sulfur breakthrough to be less than 10 ppbv in the case of natural gas, and less than 150 ppbv for LPG. We used a simulated natural gas and LPG mixture, doped with a 50-170 ppmv sulfur compound containing equal concentrations of COS, ethylmercaptan, dimethylsulfide, methylethylsulfide and tetrahydrothiophene. There is no need for recycled H 2 as in the case for hydrodesulfurization.

  17. A green surfactant-assisted synthesis of hierarchical TS-1 zeolites with excellent catalytic properties for oxidative desulfurization.

    Science.gov (United States)

    Du, Shuting; Li, Fen; Sun, Qiming; Wang, Ning; Jia, Mingjun; Yu, Jihong

    2016-02-25

    Hierarchical TS-1 zeolites with uniform intracrystalline mesopores have been successfully synthesized through the hydrothermal method by using the green and cheap surfactant Triton X-100 as the mesoporous template. The resultant materials exhibit remarkably enhanced catalytic activity in oxidative desulfurization reactions compared to the conventional TS-1 zeolite.

  18. 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…

  19. 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

  20. 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) crystals...... to discuss the potential and limitation of this technique in catalysis and related areas. With respect to the noble metal catalysed partial oxidation of methane, several interesting observations were made: structural changes during ignition were-independent of the chosen reaction conditions......-significantly faster than during the extinction of the reaction. The dynamic behavior of the catalysts was dependent on the flow conditions and the respective noble metal component(s). Higher reaction gas flow led to a faster ignition process. While the ignition over Pt-Rh/Al2O3 occurred at lower temperature than over...

  1. 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...... catalysts which has been observed and studied since the 1980s; however, despite it being interpreted differently by different research groups, there is still no decisive conclusion on the origin of the synergy effect that has been obtained. The starting idea of this work is to find an answer......, impregnation, and sol-gel methods. The mixtures were characterized by XRD, BET, XPS, and EDX techniques to determine the phase composition and surface properties. The conductivities of these samples were recorded at the catalytic reaction temperature (300-450 degrees C). Comparison of the catalytic activities...

  2. 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

  3. 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.

  4. Structural/surface characterization and catalytic evaluation of rare-earth (Y, Sm and La) doped ceria composite oxides for CH{sub 3}SH catalytic decomposition

    Energy Technology Data Exchange (ETDEWEB)

    He, Dedong; Chen, Dingkai; Hao, Husheng; Yu, Jie; Liu, Jiangping; Lu, Jichang; Liu, Feng [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Wan, Gengping [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China); Research Center for Analysis and Measurement, Hainan University, Haikou, 570228 (China); He, Sufang [Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming, 650093 (China); Luo, Yongming, E-mail: environcatalysis222@yahoo.com [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500 (China)

    2016-12-30

    Highlights: • Ce{sub 0.75}RE{sub 0.25}O{sub 2-δ} (RE = Y, Sm and La) were synthesized by citrate complexation method. • Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ} exhibited the best stability for the decomposition of CH{sub 3}SH. • Cation radius played a key role in determining structure and surface characteristics. • Catalytic behavior depended on synergistic role of oxygen vacancies and basic sites. • Ce{sub 2}S{sub 3} accumulation on the surface was responsible for the deactivation of catalyst. - Abstract: A series of rare earth (Y, Sm and La) doped ceria composite oxides and pure CeO{sub 2} were synthesized and evaluated by conducting CH{sub 3}SH catalytic decomposition test. Several characterization studies, including XRD, BET, Raman, H{sub 2}-TPR, XPS, FT-IR, CO{sub 2}-TPD and CH{sub 3}SH-TPD, were undertaken to correlate structural and surface properties of the obtained ceria-based catalysts with their catalytic performance for CH{sub 3}SH decomposition. More oxygen vacancies and increased basic sites exhibited in the rare earth doped ceria catalysts. Y doped ceria sample (Ce{sub 0.75}Y{sub 0.25}O{sub 2-δ}), with a moderate increase in basic sites, contained more oxygen vacancies. More structural defects and active sites could be provided, and a relatively small amount of sulfur would accumulate, which resulted in better catalytic performance. The developed catalyst presented good catalytic behavior with stability very similar to that of typical zeolite-based catalysts reported previously. However, La doped ceria catalyst (Ce{sub 0.75}La{sub 0.25}O{sub 2-δ}) with the highest alkalinity was not the most active one. More sulfur species would be adsorbed and a large amount of cerium sulfide species (Ce{sub 2}S{sub 3}) would accumulate, which caused deactivation of the catalysts. The combined effect of increased oxygen vacancies and alkalinity led to the catalytic stability of Ce{sub 0.75}Sm{sub 0.25}O{sub 2-δ} sample was comparable to that of pure Ce

  5. 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...

  6. Treatment of ammonia by catalytic wet oxidation process over platinum-rhodium bimetallic catalyst in a trickle-bed reactor: effect of pH.

    Science.gov (United States)

    Hung, Chang-Mao; Lin, Wei-Bang; Ho, Ching-Lin; Shen, Yun-Hwei; Hsia, Shao-Yi

    2010-08-01

    This work adopted aqueous solutions of ammonia for use in catalytic liquid-phase reduction in a trickle-bed reactor with a platinum-rhodium bimetallic catalyst, prepared by the co-precipitation of chloroplatinic acid (H2PtCl6) and rhodium nitrate [Rh(NO3)3]. The experimental results demonstrated that a minimal amount of ammonia was removed from the solution by wet oxidation in the absence of any catalyst, while approximately 97.0% of the ammonia was removed by wet oxidation over the platinum-rhodium bimetallic catalyst at 230 degrees C with an oxygen partial pressure of 2.0 MPa. The oxidation of ammonia has been studied as a function of pH, and the main reaction products were determined. A synergistic effect is manifest in the platinum-rhodium bimetallic structure, in which the material has the greatest capacity to reduce ammonia. The reaction pathway linked the oxidizing ammonia to nitric oxide, nitrogen, and water.

  7. Catalytic oxidation of 2-aminophenols and ortho hydroxylation of aromatic amines by tyrosinase

    International Nuclear Information System (INIS)

    Toussaint, O.; Lerch, K.

    1987-01-01

    The usual substrates of tyrosinase, a copper-containing monooxygenase (EC 1.14.18.1), are monophenols and o-diphenols which are both converted to o-quinones. In this paper, the authors studied the reaction of this enzyme with two new classes of substrates: aromatic amines and o-aminophenols, structural analogues of monophenols and o-diphenols, respectively. They undergo the same catalytic reactions (ortho hydroxylation and oxidation), as documented by product analysis and kinetic studies. In the presence of tyrosinase, arylamines and o-aminophenols are converted to o-quinone imines, which are isolated as quinone anils or phenoxazones. As an example, in the presence of tyrosinase, 2-amino-3-hydroxybenzoic acid (an o-aminophenol) is converted to cinnabarinic acid, a well-known phenoxazone, while p-aminotoluene (an aromatic amine) gives rise to the formation of 5-amino-2-methyl-1,4-benzoquinone 1-(4-methylanil). Kinetic studies using an oxygen electrode show that arylamines and the corresponding monophenols exhibit similar Michaelis constants. In contrast, the reaction rates observed for aromatic amines are relatively slow as compared to monophenols. The enzymatic conversion of arylamines by tryosinase is different from the typical ones: N-oxidation and ring hydroxylation without further oxidation. This difference originates from the regiospecific hydroxylation (ortho position) and subsequent oxidation of the intermediate o-aminophenol to the corresponding o-quinone imine. Finally, the well-know monooxygenase activity of tyrosinase was also confirmed for the aromatic amine p-aminotoluene, with 18 O 2

  8. 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.

  9. Rare earth oxide aero- and xerogels. Tuning porosity and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Neumann, Bjoern

    2013-11-15

    Heterogeneous catalysts to this day are still largely developed on the basis of trial and error. This is due to the great difficulty of creating custom-designed structures at the nanometer scale using traditional preparation methods. In the course of recent rapid developments in the material sciences, however, it has become possible to create materials with custom-designed properties from the macroscopic down into the nanometer range. The purpose of the present study was to make use of this potential for catalysis. The task was to modify the porosity and composition of selected rare earth oxides that promise well as catalysts with the goal of obtaining good results in terms of oxidative reactions and oxidative coupling. One major focus was on chemical sol-gel methods and in particular on what is referred to as the epoxide addition method. Extensive work was put into the characterisation and catalytic testing of aerogels and xerogels of pure rare earth oxides as well as of hybrid systems of rare earth oxides and aluminium oxide. Furthermore, thin xerogel films and macroporous monoliths were produced, the latter using a direct foaming method. The results of this work confirm the high potential of sol-gel chemistry for making porous materials of variable and controllable porosity and composition available for heterogeneous catalysis and creating more powerful catalysts. [German] Bis heute werden heterogene Katalysatoren ueberwiegend per ''trial and error'' entwickelt. Dies liegt daran, dass es mit Hilfe der traditionellen Herstellungsmethoden sehr schwierig ist, auf der Nanometerskala Strukturen gezielt herzustellen. Im Zuge der rasanten Entwicklungen in den Materialwissenschaften ist es jedoch moeglich geworden, verschiedenste Materialen mit massgeschneiderten Eigenschaften vom makroskopischen bis hinein in den Nanometerbereich herzustellen. Ziel dieser Arbeit war es, dieses Potential fuer die Katalyse zu nutzen. Dabei bestand die Aufgabe darin

  10. 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

  11. 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

  12. 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.

  13. Spectrophotometric determination of nitrite by its catalytic effect on the oxidation of congo red with bromate

    Directory of Open Access Journals (Sweden)

    Zenovia Moldovan

    2012-08-01

    Full Text Available A novel simple, sensitive and rapid kinetic-spectrophotometric method for the determination of trace amounts of nitrite is proposed. The method is based on its catalytic effect on the oxidation of congo red (CR by potassium bromate in acidic solution. The oxidation reaction is monitored spectrophotometrically by measuring the decrease in the absorbance of CR at a suitable λmax = 570 nm for the first 10–40 s from the start of the reaction. Under the optimum experimental conditions (sulfuric acid, 0.3 M; CR, 0.75Χ10-4 M; potassium bromate, 5Χ10-4 M and 25 oC, nitrite can be determined in the range of 0.015–0.75 µg mL−1 with the detection limit of 0.006 µg mL−1. The relative standard deviation of five replicate determination of 0.25 µg mL−1 nitrite was 2.5%. The proposed method was applied satisfactorily to the determination of nitrite in spiked drinking water samples.DOI: http://dx.doi.org/10.4314/bcse.v26i2.1

  14. Alumina- and titania-based monolithic catalysts for low temperature selective catalytic reduction of nitrogen oxides

    International Nuclear Information System (INIS)

    Blanco, J.; Avila, P.; Suarez, S.; Martin, J.A.; Knapp, C.

    2000-01-01

    The selective catalytic reduction of NO+NO 2 (NO x ) at low temperature (180-230C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH 3 /NO x and NO/NO 2 inlet ratios has been studied. High NO x conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N 2 O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNO x activity, with no detectable ammonia slip and a low N 2 O formation when NH 3 /NO x inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH 3 /O 2 , NO 2 /NH 3 /O 2 and NO/NO 2 /NH 3 /O 2 feed mixtures indicated that the presence of NO 2 as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N 2 O formation. When NO was also present, N 2 O formation was not observed

  15. Positron age-momentum correlation in metal oxide powders as catalytic materials

    International Nuclear Information System (INIS)

    Kishimoto, Y.; Ito, K.; Tanigawa, S.; Tsuda, N.

    1982-01-01

    Annihilation characteristics of positrons in fine particles of various types of metal oxides (MgO, SiO 2 , #betta#-Al 2 O 3 , TiO 2 , ZnO and NiO) were studied by the two parameter correlation measurements between the positron age and the momentum of annihilating pairs. It was found that the momentum dependence of lifetime can be classified into three types, that is, the bell shape tau-E relation (Type I : #betta#-Al 2 O 3 ), the W-like one (Type II : ZnO, NiO, MgO and TiO 2 ) and the M-like one (Type III : SiO 2 ). This variation may be due to the difference in the formation and reaction of positroniums at the surface of fine particles of different oxides reflecting the nature of acid points or basic points in catalytic reactions. Particularly, the frequent occurrence of the conversion process of ortho-Ps was observed. (Auth.)

  16. Reduction of nitrogen oxides from simulated exhaust gas by using plasma-catalytic process

    International Nuclear Information System (INIS)

    Mok, Young Sun; Koh, Dong Jun; Shin, Dong Nam; Kim, Kyong Tae

    2004-01-01

    Removal of nitrogen oxides (NO x ) using a nonthermal plasma reactor (dielectric-packed bed reactor) combined with monolith V 2 O 5 /TiO 2 catalyst was investigated. The effect of initial NO x concentration, feed gas flow rate (space velocity), humidity, and reaction temperature on the removal of NO x was examined. The plasma reactor used can be energized by either ac or pulse voltage. An attempt was made to utilize the electrical ignition system of an internal combustion engine as a high-voltage pulse generator for the plasma reactor. When the plasma reactor was energized by the electrical ignition system, NO was readily oxidized to NO 2 . Performance was as good as with ac energization. Increasing the fraction of NO 2 in NO x , which is the main role of the plasma reactor, largely enhanced the NO x removal efficiency. In the plasma-catalytic reactor, the increases in initial NO x concentration, space velocity (feed gas flow rate) and humidity lowered the NO x removal efficiency. However, the reaction temperature in the range up to 473 K did not significantly affect the NO x removal efficiency in the presence of plasma discharge

  17. L-proline-based deep eutectic solvents (DESs) for deep catalytic oxidative desulfurization (ODS) of diesel.

    Science.gov (United States)

    Hao, Lingwan; Wang, Meiri; Shan, Wenjuan; Deng, Changliang; Ren, Wanzhong; Shi, Zhouzhou; Lü, Hongying

    2017-10-05

    A series of L-proline-based DESs was prepared through an atom economic reaction between L-proline (L-Pro) and four different kinds of organic acids. The DESs were characterized by Fourier transform infrared spectroscopy (FT-IR), H nuclear magnetic resonance ( 1 HNMR), cyclic voltammogram (CV) and the Hammett method. The synthesized DESs were used for the oxidative desulfurization and the L-Pro/p-toluenesultonic acid (L-Pro/p-TsOH) system shows the highest catalytic activity that the removal of dibenzothiophene (DBT) reached 99% at 60°C in 2h, which may involve the dual activation of the L-Pro/p-TsOH. The acidity of four different L-proline-based DESs was measured and the results show that it could not simply conclude that the correlation between the acidity of DESs and desulfurization capability was positive or negative. The electrochemical measurements evidences and recycling experiment indicate a good stability performance of L-Pro/p-TsOH in desulfurization. This work will provide a novel and potential method for the deep oxidation desulfurization. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications.

    Science.gov (United States)

    Dong, Wenjun; Huang, Huandi; Zhu, Yanjun; Li, Xiaoyun; Wang, Xuebin; Li, Chaorong; Chen, Benyong; Wang, Ge; Shi, Zhan

    2012-10-26

    A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide-amine intermediate and Ag(+) at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO(3) nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag-MoO(3) nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature.

  19. Phosphotungstic acid encapsulated in the mesocages of amine-functionalized metal-organic frameworks for catalytic oxidative desulfurization.

    Science.gov (United States)

    Wang, Xu-Sheng; Huang, Yuan-Biao; Lin, Zu-Jin; Cao, Rong

    2014-08-21

    Highly dispersed Keggin-type phosphotungstic acid (H3PW12O40, PTA) encapsulated in the mesocages of amine-functionalized metal-organic frameworks MIL-101(Cr)-NH2 has been prepared by an anion-exchange method. PTA anions (PW12O40(3-)) are stabilized in the mesocages via the electrostatic interaction with amino groups of the MIL-101(Cr)-NH2. The obtained catalyst (denoted PTA@MIL-101(Cr)-NH2) exhibits high catalytic activity in the extractive and catalytic oxidative desulfurization (ECODS) system under mild conditions. Moreover, it can be easily recovered and recycled several times without leaching and loss of activity.

  20. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    Science.gov (United States)

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  1. 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.

  2. 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.)

  3. 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.)

  4. Predicting CYP2C19 Catalytic Parameters for Enantioselective Oxidations Using Artificial Neural Networks and a Chirality Code

    Science.gov (United States)

    Hartman, Jessica H.; Cothren, Steven D.; Park, Sun-Ha; Yun, Chul-Ho; Darsey, Jerry A.; Miller, Grover P.

    2013-01-01

    Cytochromes P450 (CYP for isoforms) play a central role in biological processes especially metabolism of chiral molecules; thus, development of computational methods to predict parameters for chiral reactions is important for advancing this field. In this study, we identified the most optimal artificial neural networks using conformation-independent chirality codes to predict CYP2C19 catalytic parameters for enantioselective reactions. Optimization of the neural networks required identifying the most suitable representation of structure among a diverse array of training substrates, normalizing distribution of the corresponding catalytic parameters (kcat, Km, and kcat/Km), and determining the best topology for networks to make predictions. Among different structural descriptors, the use of partial atomic charges according to the CHelpG scheme and inclusion of hydrogens yielded the most optimal artificial neural networks. Their training also required resolution of poorly distributed output catalytic parameters using a Box-Cox transformation. End point leave-one-out cross correlations of the best neural networks revealed that predictions for individual catalytic parameters (kcat and Km) were more consistent with experimental values than those for catalytic efficiency (kcat/Km). Lastly, neural networks predicted correctly enantioselectivity and comparable catalytic parameters measured in this study for previously uncharacterized CYP2C19 substrates, R- and S-propranolol. Taken together, these seminal computational studies for CYP2C19 are the first to predict all catalytic parameters for enantioselective reactions using artificial neural networks and thus provide a foundation for expanding the prediction of cytochrome P450 reactions to chiral drugs, pollutants, and other biologically active compounds. PMID:23673224

  5. 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

  6. In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

    Science.gov (United States)

    Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

    2017-12-01

    A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

  7. 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

  8. 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

  9. Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

    Science.gov (United States)

    Opila, Elizabeth J.; Serra, Jessica

    2009-01-01

    Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

  10. Partial substitution of manganese with cerium in SrMnO_3 nano-perovskite catalyst. Effect of the modification on the catalytic combustion of dilute acetone

    International Nuclear Information System (INIS)

    Rezlescu, Nicolae; Rezlescu, Elena; Popa, Paul Dorin; Doroftei, Corneliu; Ignat, Maria

    2016-01-01

    Ultrafine SrMn_1_−_xCe_xO_3 (x = 0, 02) perovskites were prepared by self-combustion method and heat treatment at 1000 °C for 4 h. The structure and surface properties were investigated by X-ray powder diffraction, scanning electron microscopy (SEM), EDX spectroscopy, and BET analysis. The catalyst properties of the perovskite nanopowders were tested in the catalytic combustion of dilute acetone at atmospheric pressure. The results revealed that the partial substitution of Mn by Ce ions (x = 0.2) in perovskite structure of SrMnO_3 had significantly improved catalytic activity of the perovskite. The SrMn_0_._8Ce_0_,_2O_3 perovskite composition can be a good candidate for catalytic combustion of low concentration acetone (1–2‰ in air) at low temperatures. The acetone conversion over this catalyst exceeds 90% at 200 °C, whereas over SrMnO_3 it is only 50%. Compared with SrMnO_3, T_5_0 is decreased by 75 °C and T_9_0 is decreased by 70 °C. The enhancement of the catalytic activity at a Ce doping of 0.2 may be ascribed to smaller crystallite sizes, larger specific surface area and the presence of Ce and Mn cations with variable valence in the perovskite structure. - Highlights: • A non-conventional method was used to make nanostructured perovskite samples. • XRD study confirms perovskite structure and nanosize of crystallites. • EDX analyses confirm homogeneity and purity of the samples. • The catalytic testing was carried out in the flameless combustion of dilute acetone. • SrMn_0_._8Ce_0_._2O_3 perovskite can be a promising catalyst for acetone combustion at low temperature.

  11. Partial substitution of manganese with cerium in SrMnO{sub 3} nano-perovskite catalyst. Effect of the modification on the catalytic combustion of dilute acetone

    Energy Technology Data Exchange (ETDEWEB)

    Rezlescu, Nicolae, E-mail: nicolae.rezlescu@gmail.com [National Institute of Research and Development for Technical Physics, Iasi (Romania); Rezlescu, Elena; Popa, Paul Dorin; Doroftei, Corneliu [National Institute of Research and Development for Technical Physics, Iasi (Romania); Ignat, Maria [“Al. I. Cuza” University, Faculty of Chemistry, Iasi (Romania)

    2016-10-01

    Ultrafine SrMn{sub 1−x}Ce{sub x}O{sub 3} (x = 0, 02) perovskites were prepared by self-combustion method and heat treatment at 1000 °C for 4 h. The structure and surface properties were investigated by X-ray powder diffraction, scanning electron microscopy (SEM), EDX spectroscopy, and BET analysis. The catalyst properties of the perovskite nanopowders were tested in the catalytic combustion of dilute acetone at atmospheric pressure. The results revealed that the partial substitution of Mn by Ce ions (x = 0.2) in perovskite structure of SrMnO{sub 3} had significantly improved catalytic activity of the perovskite. The SrMn{sub 0.8}Ce{sub 0,2}O{sub 3} perovskite composition can be a good candidate for catalytic combustion of low concentration acetone (1–2‰ in air) at low temperatures. The acetone conversion over this catalyst exceeds 90% at 200 °C, whereas over SrMnO{sub 3} it is only 50%. Compared with SrMnO{sub 3}, T{sub 50} is decreased by 75 °C and T{sub 90} is decreased by 70 °C. The enhancement of the catalytic activity at a Ce doping of 0.2 may be ascribed to smaller crystallite sizes, larger specific surface area and the presence of Ce and Mn cations with variable valence in the perovskite structure. - Highlights: • A non-conventional method was used to make nanostructured perovskite samples. • XRD study confirms perovskite structure and nanosize of crystallites. • EDX analyses confirm homogeneity and purity of the samples. • The catalytic testing was carried out in the flameless combustion of dilute acetone. • SrMn{sub 0.8}Ce{sub 0.2}O{sub 3} perovskite can be a promising catalyst for acetone combustion at low temperature.

  12. 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.

  13. Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

    Science.gov (United States)

    You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

    2010-05-01

    Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

  14. 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.

  15. [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.

  16. 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.

  17. 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.

  18. 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.

  19. Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

    Energy Technology Data Exchange (ETDEWEB)

    Haw, Kok-Giap; Bakar, Wan Azelee Wan Abu; Ali, Rusmidah; Chong, Jiunn-Fat [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia); Kadir, Abdul Aziz Abdul [Department of Petroleum Engineering, Faculty of Chemical and Natural Resources Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2010-09-15

    This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 C and 700 C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H{sub 2}O{sub 2}/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed. (author)

  20. Effect of oxygen partial pressure on oxidation of Mo-metal

    Science.gov (United States)

    Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

    2018-05-01

    This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

  1. Stereoselectivity in catalytic reactions: CO oxidation on Pd(100) by rotationally aligned O2 molecules

    Science.gov (United States)

    Vattuone, L.; Gerbi, A.; Savio, L.; Cappelletti, D.; Pirani, F.; Rocca, M.

    2010-05-01

    We report on stereodynamical effects in heterogeneous catalytic reactions as measured by molecular beam-surface experiments. Specifically for CO oxidation on Pd(100) we find that the rotational alignment of the incoming O2 at low (Θ = 0.04 ML) and at intermediate (ΘCO = 0.17 ML) CO pre-coverage, causes a higher reactivity of molecules in high and in low helicity states, respectively (corresponding to helicoptering and cartwheeling motion of O2). In first approximation, at low CO pre-coverage the difference in reactivity is determined by the different location of the O atoms generated in the dissociation process by the different parent molecules, while at intermediate CO pre-coverage the reactivity is influenced also by the different ability of cartwheeling and helicoptering O2 to penetrate through the CO adlayer. In accord with this the total amount of CO2 produced is always largest for helicopters which generate supersurface O atoms at least in the low CO pre-coverage limit. A deeper inspection of the data indicates, however, that the dynamics is more complex, two different pathways being present for the reaction with O generated by helicopters and one for O generated by cartwheels. Moreover, cartwheels generated oxygen influences the reactivity of subsequently arriving helicopters.

  2. 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.

  3. 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.

  4. 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

  5. The catalytic oxidation of malachite green by the microwave-Fenton processes.

    Science.gov (United States)

    Zheng, Huaili; Zhang, Huiqin; Sun, Xiaonan; Zhang, Peng; Tshukudu, Tiroyaone; Zhu, Guocheng

    2010-01-01

    Catalytic oxidation of malachite green using the microwave-Fenton process was investigated. 0% of malachite green de-colorization using the microwave process and 23.5% of malachite green de-colorization using the Fenton process were observed within 5 minutes. In contrast 95.4% of malachite green de-colorization using the microwave-Fenton was observed in 5 minutes. During the microwave-Fenton process, the optimum operating conditions for malachite green de-colorization were found to be 3.40 of initial pH, 0.08 mmol/L of Fe2+ concentration and 12.5 mmol/L of H2O2 concentration. Confirmatory tests were carried out under the optimum conditions and the COD removal rate of 82.0% and the de-colorization rate of 99.0% were observed in 5 minutes. The apparent kinetics equation of -dC/dt=0.0337 [malachite green]0.9860[Fe2+)]0.8234[H2O2]0.1663 for malachite green de-colorization was calculated, which implied that malachite green was the dominant factor in determining the removal efficiency of malachite green based on microwave-Fenton process.

  6. Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications

    International Nuclear Information System (INIS)

    Dong Wenjun; Huang Huandi; Zhu Yanjun; Li Xiaoyun; Wang Xuebin; Li Chaorong; Chen Benyong; Wang Ge; Shi Zhan

    2012-01-01

    A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide–amine intermediate and Ag + at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO 3 nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag–MoO 3 nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature. (paper)

  7. 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.

  8. Boosting the catalytic activity of natural magnetite for wet peroxide oxidation.

    Science.gov (United States)

    Álvarez-Torrellas, Silvia; Munoz, Macarena; Mondejar, Victor; de Pedro, Zahara M; Casas, Jose A

    2018-06-02

    This work explores the modification of naturally occurring magnetite by controlled oxidation (200-400 °C, air atmosphere) and reduction (300-600 °C, H 2 atmosphere) treatments with the aim of boosting its activity in CWPO. The resulting materials were fully characterized by XRD, XPS, TGA, TPR, SEM, and magnetization measurements, allowing to confirm the development of core-shell type structures. The magnetite core of the solid remained unchanged upon the treatment whereas the Fe(II)/Fe(III) ratio of the shell was modified (e.g. 0.42, 0.11 and 0.63 values were calculated for pristine Fe 3 O 4 , Fe 3 O 4 -O400, and Fe 3 O 4 -R400, respectively). The performance of the catalysts was tested in the CWPO of sulfamethoxazole (SMX) (5 mg L -1 ) under ambient conditions and circumneutral pH (pH 0  = 5), using the stoichiometric dose of H 2 O 2 (25 mg L -1 ) and a catalyst load of 1 g L -1 . The key role of the ferrous species on the mineral shell was evidenced. Whereas the oxidation of magnetite led to significantly slower degradation rates of the pollutant, its reduction gave rise to a dramatic increase, achieving the complete removal of SMX in 1.5 h reaction time with the optimum catalyst (Fe 3 O 4 -R400) compared to the 3.5 h required with the pristine mineral. A reaction mechanism was proposed for SMX degradation, and a kinetic equation based on the Eley-Rideal model was accordingly developed. This model successfully fitted the experimental results. The stability of Fe 3 O 4 -R400 was evaluated upon five sequential runs. Finally, the versatility of the catalytic system was proved in real environmentally relevant water matrices.

  9. Oxidation of winery wastewater by sulphate radicals: catalytic and solar photocatalytic activations.

    Science.gov (United States)

    Rodríguez-Chueca, Jorge; Amor, Carlos; Mota, Joana; Lucas, Marco S; Peres, José A

    2017-10-01

    The treatment of winery effluents through sulphate radical-based advanced oxidation processes (SR-AOPs) driven by solar radiation is reported in this study. Photolytic and catalytic activations of peroxymonosulphate (PMS) and persulphate (KPS and SPS) at different pH values (4.5 and 7) were studied in the degradation of organic matter. Portugal is one of the largest wine producers in Europe. The wine making activities generate huge volume of effluents characterized by a variable volume and organic load, being their seasonal nature one of the most important drawbacks. Recently, SR-AOPs are gradually attracting attention as in situ chemical oxidation technologies, instead of hydroxyl radical AOPs (HR-AOPs). The studied concentrations are suitable to obtain notable values of organic matter degradation, with TOC removal around 50%. In general terms, no notable differences were observed between treatments at pH values 4.5 and 7. Photolytic activation of SPS with solar radiation treatments obtained the highest efficiency (28 and 40% of TOC removal with 1 and 50 mM, respectively, at pH 4.5) in comparison to KPS and PMS. The addition of a transition metal as catalyst, such as Fe(II) or Co(II), increased considerably the TOC removal efficiency higher than 50%, but not in all cases. For instance, the combination KPS or PMS with Co(II) at pH 4.5 did not allow to obtain better results than photolytic activation of these persulphate salts. In summary, the use of SR-AOPs could be a serious alternative as tertiary treatment for winery wastewaters.

  10. 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)

  11. The effect of antimony-tin and indium-tin oxide supports on the catalytic activity of Pt nanoparticles for ammonia electro-oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Júlio César M. [Department of Chemical & Biological Engineering, Centre for Catalysis Research and Innovation (CCRI), University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada); Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária, CEP 05508-900, São Paulo, SP (Brazil); Piasentin, Ricardo M.; Spinacé, Estevam V.; Neto, Almir O. [Instituto de Pesquisas Energéticas e Nucleares, IPEN/CNEN-SP, Av. Prof. Lineu Prestes, 2242 Cidade Universitária, CEP 05508-900, São Paulo, SP (Brazil); Baranova, Elena A., E-mail: elena.baranova@uottawa.ca [Department of Chemical & Biological Engineering, Centre for Catalysis Research and Innovation (CCRI), University of Ottawa, 161 Louis-Pasteur, Ottawa, ON K1N 6N5 (Canada)

    2016-09-01

    Platinum nanoparticles supported on carbon (Pt/C) and carbon with addition of ITO (Pt/C-ITO (In{sub 2}O{sub 3}){sub 9}·(SnO{sub 2}){sub 1}) and ATO (Pt/C-ATO (SnO{sub 2}){sub 9}·(Sb{sub 2}O{sub 5}){sub 1}) oxides were prepared by sodium borohydride reduction method and used for ammonia electro-oxidation reaction (AmER) in alkaline media. The effect of the supports on the catalytic activity of Pt for AmER was investigated using electrochemical (cyclic voltammetry and chronoamperometry) and direct ammonia fuel cell (DAFC) experiments. X-ray diffraction (XRD) showed Pt peaks attributed to the face-centered cubic (fcc) structure, as well as peaks characteristic of In{sub 2}O{sub 3} in ITO support and cassiterite SnO{sub 2} phase of ATO support. According to transmission electron micrographs the mean particles sizes of Pt over carbon were 5.4, 4.9 and 4.7 nm for Pt/C, Pt/C-ATO and Pt/C-ITO, respectively. Pt/C-ITO catalysts showed the highest catalytic activity for ammonia electrooxidation in both electrochemical and fuel cell experiments. We attributed this to the presence of In{sub 2}O{sub 3} phase in ITO, which provides oxygenated or hydroxide species at lower potentials resulting in the removal of poisonous intermediate, i.e., atomic nitrogen (N{sub ads}) and promotion of ammonia electro-oxidation. - Highlights: • Oxide support effect on the catalytic activity of Pt towards ammonia electro-oxidation. • Direct ammonia fuel cell (DAFC) performance using Pt over different supports as anode. • Pt/C-ITO shows better catalytic activity for ammonia oxidation than Pt/C and Pt/C-ATO.

  12. 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.

  13. 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.

  14. Hydrogen storage evaluation based on investigations of the catalytic properties of metal/metal oxides in electrospun carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Im, Ji Sun; Lee, Young-Seak [Department of Fine Chemical Engineering and Chemistry, Chungnam National University, Daejeon 305-764 (Korea); Park, Soo-Jin [Department of Chemistry, Inha University, Incheon 402-751 (Korea); Kim, Taejin [Core Technology Research Center for Fuel Cell, Jeollabuk-do 561-844 (Korea)

    2009-05-15

    In order to investigate the catalytic capacity of metals and metal oxides based on electrospun carbon fibers for improving hydrogen storage, electrospinning and heat treatments were carried out to obtain metal/metal oxide-embedded carbon fibers. Although the fibers were treated with the same activation procedure, they had different pore structures, due to the nature of the metal oxide. When comparing the catalytic capacity of metal and metal oxide, metal exhibits better performance as a catalyst for the improvement of hydrogen storage, when considering the hydrogen storage system. When a metal oxide with an m.p. lower than the temperature of heat treatment was used, the metal oxide was changed to metal during the heat treatment, developing a micropore structure. The activation process produced a high specific surface area of up to 2900 m{sup 2}/g and a pore volume of up to 2.5 cc/g. The amount of hydrogen adsorption reached approximately 3 wt% at 100 bar and room temperature. (author)

  15. 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.

  16. 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.

  17. 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.

  18. Improved catalytic efficiency, thermophilicity, anti-salt and detergent tolerance of keratinase KerSMD by partially truncation of PPC domain.

    Science.gov (United States)

    Fang, Zhen; Zhang, Juan; Du, Guocheng; Chen, Jian

    2016-06-14

    The keratinase from Stenotrophomonas maltophilia (KerSMD) is known for its high activity and pH stability in keratin degradation. However, catalytic efficiency and detergent tolerability need to be improved in order to be used for industrial application. In this work, we obtained several keratinase variants with enhanced catalytic efficiency, thermophilicity, and anti-salt and detergent tolerability by partially truncating the PPC domain of KerSMD. The variants all showed improved catalytic efficiency to synthetic substrate AAPF, with the V355 variant having the highest kcat /Km value of 143.6 s(-1) mM(-1). The truncation of keratinase had little effect on alkaline stability but obviously decreased collagenase activity, developing its potential application in leather treatment. The variants V380, V370, and V355 were thermophilic, with a 1.7-fold enhancement of keratinlytic activity at 60 °C when compared to the wild type. The entire truncation of PPC domain obtained the variant V355 with improved tolerance to alkalinity, salt, chaotropic agents, and detergents. The V355 variant showed more than a 40% improvement in activity under 15% (w/v) NaCl or 4% (w/v) SDS solution, showing excellent stability under harsh washing and unhairing conditions. Our work investigated how protein engineering affects the function of PPC domain of KerSMD.

  19. 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.

  20. 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

  1. Hydrogen or synthesis gas production via the partial oxidation of methane over supported nickel-cobalt catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Alaric C.W. [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Chen, Luwei; Lin, Jianyi [Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore 627833 (Singapore); Kee Leong, Weng [Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543 (Singapore); Johnson, Brian F.G.; Khimyak, Tetyana [University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW (United Kingdom)

    2007-05-15

    Activity, selectivity, and coking-resistance of a series of Ni{sub x}Co{sub y} (where x,y are the respective metal loadings of 0, 1, 2 or 3 wt.%; x+y=3) bimetallic catalysts supported on CaAl{sub 2}O{sub 4}/Al{sub 2}O{sub 3} have been studied for hydrogen/synthesis gas production via the catalytic partial oxidation (CPO) of methane. Catalysts were characterized by temperature programmed reduction (TPR), transmission electron microscopy (TEM) and X-ray fluorescence multi-element analysis (XRF). Their activity for the partial oxidation of methane to hydrogen and carbon monoxide (at 1 bar, gas hourly space velocity (GHSV) of 144,000cm{sup 3}g{sup -1}h{sup -1} and CH{sub 4}/O{sub 2} molar ratio of 2) was investigated, and coke deposited on the spent catalysts was studied by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA). The activity was found to decrease in the order of Ni{sub 2}Co>Ni{sub 3}>NiCo{sub 2}>>Co{sub 3}, while CO and H{sub 2} selectivities were found to be in the order ofNi{sub 2}Co>Ni{sub 3}{approx}NiCo{sub 2}>Co{sub 3}. Ni{sub 2}Co is also shown to be more resistant to coking as compared to Ni{sub 3}, which is a current catalyst of choice. Results show that not only does Ni{sub 2}Co have the highest activity and selectivity among all the catalysts tested, it is also relatively resistant to coking. This finding would be helpful for catalyst design to achieve high coking resistivity catalysts for hydrogen production from CPO of methane. (author)

  2. 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.)

  3. A new approach for crystallization of copper(ii) oxide hollow nanostructures with superior catalytic and magnetic response

    Science.gov (United States)

    Singh, Inderjeet; Landfester, Katharina; Chandra, Amreesh; Muñoz-Espí, Rafael

    2015-11-01

    We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism. Electronic supplementary information (ESI) available: Associated structural and morphological analysis, XPS characterization, BET surface area, catalytic measurements, recycle tests of the catalyst, and magnetic characterizations. See DOI: 10.1039/c5nr05579b

  4. Catalytic Chan–Lam coupling using a ‘tube-in-tube’ reactor to deliver molecular oxygen as an oxidant

    Directory of Open Access Journals (Sweden)

    Carl J. Mallia

    2016-07-01

    Full Text Available A flow system to perform Chan–Lam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the re-oxidation of the copper catalyst enabling a catalytic process. A tube-in-tube gas reactor has been used to simplify the delivery of the oxygen accelerating the optimisation phase and allowing easy access to elevated pressures. A small exemplification library of heteroaromatic products has been prepared and the process has been shown to be robust over extended reaction times.

  5. Synergy of iron and copper oxides in the catalytic formation of PCDD/Fs from 2-monochlorophenol.

    Science.gov (United States)

    Potter, Phillip M; Guan, Xia; Lomnicki, Slawomir M

    2018-07-01

    Transition metal oxides present in waste incineration systems have the ability to catalyze the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through surface reactions involving organic dioxin precursors. However, studies have concentrated on the catalytic effects of individual transition metal oxides, while the complex elemental composition of fly ash introduces the possibility of synergistic or inhibiting effects between multiple, catalytically active components. In this study, we have tested fly ash surrogates containing different ratios (by weight) of iron (III) oxide and copper (II) oxide. Such Fe 2 O 3 /CuO mixed-oxide surrogates (in the Fe:Cu ratio of 3.5, 0.9 and 0.2 ) were used to study the cooperative effects between two transition metals that are present in high concentrations in most combustion systems and are known to individually catalyze the formation of PCDD/Fs. The presence of both iron and copper oxides increased the oxidative power of the fly ash surrogates in oxygen rich conditions and led to extremely high PCDD/F yields under pyrolytic conditions (up to >5% yield) from 2-monochlorophenol precursor. PCDD/F congener profiles from the mixed oxide samples are similar to results obtained from only CuO, however the total PCDD/F yield increases with increasing Fe 2 O 3 content. Careful analysis of the reaction products and changes to the oxidation states of active metals indicate the CuO surface sites are centers for reaction while the Fe 2 O 3 is affecting the bonds in CuO and increasing the ability of copper centers to form surface-bound radicals that are precursors to PCDD/Fs. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. 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.

  7. Catalytic properties of new anode materials for solid oxide fuel cells operated under methane at intermediary temperature

    Science.gov (United States)

    Sauvet, A.-L.; Fouletier, J.

    The recent trend in solid oxide fuel cell concerns the use of natural gas as fuel. Steam reforming of methane is a well-established process for producing hydrogen directly at the anode side. In order to develop new anode materials, the catalytic activities of several oxides for the steam reforming of methane were characterized by gas chromatography. We studied the catalytic activity as a function of steam/carbon ratios r. The methane and the steam content were varied between 5 and 30% and between 1.5 and 3.5%, respectively, corresponding to r-values between 0.07 and 0.7. Catalyst (ruthenium and vanadium)-doped lanthanum chromites substituted with strontium, gadolinium-doped ceria (Ce 0.9Gd 0.1O 2) referred as to CeGdO 2, praseodymium oxide, molybdenum oxide and copper oxide were tested. The working temperature was fixed at 850°C, except for 5% ruthenium-doped La 1- xSr xCrO 3 where the temperature was varied between 700 and 850°C. Two types of behavior were observed as a function of the activity of the catalyst. The higher steam reforming efficiency was observed with 5% of ruthenium above 750°C.

  8. 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.)

  9. Reaction scheme of partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia

    NARCIS (Netherlands)

    Zhu, J.J.; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    The partial oxidation of methane to synthesis gas over yttrium-stabilized zirconia (YSZ) was studied with in situ FTIR and both steady-state and transient experiments. The four major products, CO, H2, CO2, and H2O, are primary products of CPOM over YSZ. Besides these major products and traces of

  10. 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

    adsorption and determined by stable isotope dilution analysis. The results have shown that partial oxidation reduces and converts primary tars into low molecular weight, polycyclic aromatic hydrocarbons (PAHs), primarily naphthalene. At temperatures above 950°C practically all phenol is converted...

  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.; Sint Annaland, van 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. 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

  15. 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

  16. Development of a simultaneous partial nitrification and anaerobic ammonia oxidation process in a single reactor.

    Science.gov (United States)

    Cho, Sunja; Fujii, Naoki; Lee, Taeho; Okabe, Satoshi

    2011-01-01

    Up-flow oxygen-controlled biofilm reactors equipped with a non-woven fabric support were used as a single reactor system for autotrophic nitrogen removal based on a combined partial nitrification and anaerobic ammonium oxidation (anammox) reaction. The up-flow biofilm reactors were initiated as either a partial nitrifying reactor or an anammox reactor, respectively, and simultaneous partial nitrification and anammox was established by careful control of the aeration rate. The combined partial nitrification and anammox reaction was successfully developed in both biofilm reactors without additional biomass inoculation. The reactor initiated as the anammox reactor gave a slightly higher and more stable mean nitrogen removal rate of 0.35 (±0.19) kg-N m(-3) d(-1) than the reactor initiated as the partial nitrifying reactor (0.23 (±0.16) kg-N m(-3) d(-1)). FISH analysis revealed that the biofilm in the reactor started as the anammox reactor were composed of anammox bacteria located in inner anoxic layers that were surrounded by surface aerobic AOB layers, whereas AOB and anammox bacteria were mixed without a distinguishable niche in the biofilm in the reactor started as the partial nitrifying reactor. However, it was difficult to efficiently maintain the stable partial nitrification owing to inefficient aeration in the reactor, which is a key to development of the combined partial nitrification and anammox reaction in a single biofilm reactor. Copyright © 2010 Elsevier Ltd. All rights reserved.

  17. Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

    Science.gov (United States)

    Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

    2016-05-17

    Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and

  18. 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.

  19. 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.

  20. Catalytic decomposition of nitrous oxide from nitric acid production tail gases. Investigation of inhibition effects. Executive summary

    International Nuclear Information System (INIS)

    Mul, G.; Perez-Ramirez, J.; Xu, Xiaoding; Oonk, H.; Yakovlev, A.

    2001-06-01

    Nitric acid production is an important source of nitrous oxide, one of the green-house gases. Catalytic decomposition of N2O in nitric acid tail-gases might be a possibility for emission reduction, but technology is not yet available. As a part of development of suitable catalytic systems, research was performed, aiming at: gaining an improved understanding of catalytic decomposition of N2O and the inhibiting effects of NO, NO2, H2O and O2; and preparing a 'go-no go' decision whether or not to proceed with subsequent re-search and development and if yes, to indicate what technology further development should aim for. Due to the presence of NOx and water in the nitric acid tail gases, catalytic decomposition proves not to be feasible at temperatures below 350C. At higher temperatures possibilities do exist and a number of promising catalysts are identified. These are active (80 - 100 % conversion) in the temperature range of 400 - 500C and under simulated tail gas conditions. Considering process conditions only (temperatures and composition of the tail-gases), the catalysts studied (pref. the Rh/Al2O3 types) could be in principle applied successfully in all Dutch nitric acid plants

  1. EMISSION REDUCTION FROM A DIESEL ENGINE FUELED BY CERIUM OXIDE NANO-ADDITIVES USING SCR WITH DIFFERENT METAL OXIDES COATED CATALYTIC CONVERTER

    Directory of Open Access Journals (Sweden)

    B. JOTHI THIRUMAL

    2015-11-01

    Full Text Available This paper reports the results of experimental investigations on the influence of the addition of cerium oxide in nanoparticle form on the major physiochemical properties and the performance of diesel. The fuel is modified by dispersing the catalytic nanoparticle by ultrasonic agitation. The physiochemical properties of sole diesel fuel and modified fuel are tested with ASTM standard procedures. The effects of the additive nanoparticles on the individual fuel properties, the engine performance, and emissions are studied, and the dosing level of the additive is optimized. Cerium oxide acts as an oxygen-donating catalyst and provides oxygen for the oxidation of CO during combustion. The active energy of cerium oxide acts to burn off carbon deposits within the engine cylinder at the wall temperature and prevents the deposition of non-polar compounds on the cylinder wall which results in reduction in HC emission by 56.5%. Furthermore, a low-cost metal oxide coated SCR (selective catalyst reduction, using urea as a reducing agent, along with different types of CC (catalytic converter, has been implemented in the exhaust pipe to reduce NOx. It was observed that a reduction in NOx emission is 50–60%. The tests revealed that cerium oxide nanoparticles can be used as an additive in diesel to improve complete combustion of the fuel and reduce the exhaust emissions significantly.

  2. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Kootenaei, A.H. Shahbazi; Towfighi, J.; Khodadadi, A.; Mortazavi, Y.

    2014-01-01

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V 2 O 5 catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere

  3. Ultrasensitive colorimetric detection of Cu2+ ion based on catalytic oxidation of L-cysteine.

    Science.gov (United States)

    Yin, Kun; Li, Bowei; Wang, Xiaochun; Zhang, Weiwei; Chen, Lingxin

    2015-02-15

    As an essential element, copper ion (Cu(2+)) plays important roles in human beings for its participation in diverse metabolic processes as a cofactor and/or a structural component of enzymes. However, excessive uptake of Cu(2+) ion gives rise to the risk of certain diseases. So, it is important to develop simple ways to monitor and detect Cu(2+) ion. In this study, a simple, facile colorimetric sensor for the ultrasensitive determination of Cu(2+) ion was developed based on the following principle: L-cysteine and 1-chloro-2,4-dinitrobenzene (CDNB) could be conjugated to form the yellow product 2,4-dinitrophenylcysteine (DNPC), which was measurable at 355nm; however, upon addition of Cu(2+) ion, the absorbance of DNPC would be decreased owing to the Cu(2+) ion catalytic oxidation of L-cysteine to L-cystine in the presence of O2. Thus, the colorimetric detection of Cu(2+) ion could be achieved. The optimal pH, buffer, temperature and incubation time for the colorimetric sensor were obtained of pH 6.8 in 0.1M HEPES solution, 90 °C and 50 min, respectively. A good linearity within the range of 0.8-10 nM (r = 0.996) was attained, with a high detectability up to 0.5nM. Analyses of Cu(2+) ion in drinking water, lake water, seawater and biological samples were carried out and the method performances were found to agree well with that obtained by ICP-MS. The developed simple colorimetric sensor proved applicable for Cu(2+) ion determination in real samples with high sensitivity and selectivity. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Kootenaei, A.H. Shahbazi [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Towfighi, J., E-mail: towfighi@modares.ac.ir [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Khodadadi, A.; Mortazavi, Y. [Catalysis and Nanostructured Materials Laboratory, Oil and Gas Processing Center of Excellence, Department of Chemical Engineering, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran (Iran, Islamic Republic of)

    2014-04-01

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V{sub 2}O{sub 5} catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere.

  5. Biological degradation of partially oxidated constituents of stabilized sapropel; Biologischer Abbau teiloxidierter Inhaltsstoffe stabilisierter Faulschlaemme

    Energy Technology Data Exchange (ETDEWEB)

    Scheminski, A.; Krull, R.; Hempel, D.C. [Technische Univ. Braunschweig (Germany). Inst. fuer Bioverfahrenstechnik

    1999-07-01

    Partial oxidation of sapropel with ozone destroys the cell walls of microorganisms in sludge and releases the cell constituents. Substances that are not biologically degraded because of the size or structure of their molecules are transformed into smaller, water-soluble and biologically degradable fractions by the reaction with ozone. The experiments aim to render the partially oxidated sewage sludge constituents highly biologically degradable using a minimum of oxidation agents. For the experiments described, stabilized sapropels with low biological activity are used. Hence the ozone is mainly used for the partial oxidation of recalcitrant constituents. (orig.) [German] Durch partielle Oxidation von Faulschlaemmen mit Ozon werden die Zellwaende der Mikroorganismen im Schlamm zerstoert und die Zellinhaltsstoffe freigesetzt. Dabei werden Substanzen, die aufgrund ihrer Molekuelgroesse oder -struktur biologisch nicht abgebaut werden, durch die Reaktion mit Ozon in kleinere, wasserloesliche und biologisch abbaubare Bruchstuecke ueberfuehrt. Ziel der Versuche ist es, durch den Einsatz moeglichst geringer Mengen an Oxidationsmitteln eine hohe biologische Abbaubarkeit der teiloxidierten Klaerschlamminhaltsstoffe zu erreichen. Fuer die hier vorgestellten Experimente wurden stabilisierte Faulschlaemme mit geringer biologischer Aktivitaet eingesetzt. Dadurch wird das Ozon vorwiegend zur Teiloxidation recalcitranter Inhaltsstoffe genutzt. (orig.)

  6. Trapping and partial characterization of an adduct postulated to be the covalent catalytic ternary complex of thymidylate synthetase

    International Nuclear Information System (INIS)

    Ahmed, F.; Moore, M.A.; Dunlap, R.B.

    1986-01-01

    The proposed mechanism of action of thymidylate synthetase envisages the formation of a covalent ternary complex of the enzyme via the active site cysteine with dUMP and 5,10-methylenetetrahydrofolate (CH 2 H 4 folate). The authors recent success in using trichloroacetic acid to trap the covalent enzyme-FdUMP binary and ternary (enzyme-FdUMP-CH 2 H 4 folate) complexes led to the use of this technique in attempts to trap the transient covalent catalytic ternary complex. Experiments performed with [2-C 14 ]dUMP and 3 H-CH 2 H 4 folate show that both these ligands remained bound to the enzyme after trichloroacetic acid precipitation. The trapped covalent catalytic ternary complex was subjected to CNBr fragmentation, and the peptides were fractionated by HPLC. The isolated active-site peptide was shown to retain the two ligands and was subjected to a limited sequence analysis by the dansyl-Edman procedure. The inhibitory ternary complex formed with 14 C-FdUMP and 3 H-CH 2 4 folate served as a control. The active-site peptides isolated from the CNBr treated inhibitory ternary complex and the catalytic complex exhibited identical sequences for the first four N-terminal residues, Ala-Leu-Pro-Pro, and the fifth residue was found to be associated with the labeled ligands. Sequence analysis of the active site peptide derived from the carboxymethylated enzyme confirmed this sequence and the 5th residue was shown to be Cm-Cys

  7. Trapping and partial characterization of an adduct postulated to be the covalent catalytic ternary complex of thymidylate synthetase

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, F.; Moore, M.A.; Dunlap, R.B.

    1986-05-01

    The proposed mechanism of action of thymidylate synthetase envisages the formation of a covalent ternary complex of the enzyme via the active site cysteine with dUMP and 5,10-methylenetetrahydrofolate (CH/sub 2/H/sub 4/folate). The authors recent success in using trichloroacetic acid to trap the covalent enzyme-FdUMP binary and ternary (enzyme-FdUMP-CH/sub 2/H/sub 4/folate) complexes led to the use of this technique in attempts to trap the transient covalent catalytic ternary complex. Experiments performed with (2-C/sup 14/)dUMP and /sup 3/H-CH/sub 2/H/sub 4/folate show that both these ligands remained bound to the enzyme after trichloroacetic acid precipitation. The trapped covalent catalytic ternary complex was subjected to CNBr fragmentation, and the peptides were fractionated by HPLC. The isolated active-site peptide was shown to retain the two ligands and was subjected to a limited sequence analysis by the dansyl-Edman procedure. The inhibitory ternary complex formed with /sup 14/C-FdUMP and /sup 3/H-CH/sub 2/ /sub 4/folate served as a control. The active-site peptides isolated from the CNBr treated inhibitory ternary complex and the catalytic complex exhibited identical sequences for the first four N-terminal residues, Ala-Leu-Pro-Pro, and the fifth residue was found to be associated with the labeled ligands. Sequence analysis of the active site peptide derived from the carboxymethylated enzyme confirmed this sequence and the 5th residue was shown to be Cm-Cys.

  8. Mammalian α-polymerase: cloning of partial complementary DNA and immunobinding of catalytic subunit in crude homogenate protein blots

    International Nuclear Information System (INIS)

    SenGupta, D.N.; Kumar, P.; Zmudzka, B.Z.; Coughlin, S.; Vishwanatha, J.K.; Robey, F.A.; Parrott, C.; Wilson, S.H.

    1987-01-01

    A new polyclonal antibody against the α-polymerase catalytic polypeptide was prepared by using homogeneous HeLa cellα-polymerase. The antibody neutralized α-polymerase activity and was strong and specific for the α-polymerase catalytic polypeptide (M/sub r/ 183,000) in Western blot analysis of crude extracts of HeLa cells. The antibody was used to screen a cDNA library of newborn rat brain poly(A+) RNA in λgt11. A positive phage was identified and plaque purified. This phage, designated λpolα1.2, also was found to be positive with an antibody against Drosophila α-polymerase. The insert in λpolα1.2 (1183 base pairs) contained a poly(A) sequence at the 3' terminus and a short in-phase open reading frame at the 5' terminus. A synthetic oligopeptide (eight amino acids) corresponding to the open reading frame was used to raise antiserum in rabbits. Antibody affinity purified from this serum was found to be immunoreactive against purified α-polymerase by enzyme-linked immunosorbent assay and was capable of immunoprecipitating α-polymerase. This indicated the λpolα1.2 insert encoded an α-polymerase epitope and suggested that the cDNA corresponded to an α-polymerase mRNA. This was confirmed in hybrid selection experiments using pUC9 containing the cDNA insert and poly(A+) RNA from newborn rat brain; the insert hybridized to mRNA capable of encoding α-polymerase catalytic polypeptides. Northern blot analysis of rat brain poly(A+) RNA revealed that this mRNA is ∼5.4 kilobases

  9. One-Pot Synthesis of Cu(II Complex with Partially Oxidized TTF Moieties

    Directory of Open Access Journals (Sweden)

    Hiroki Oshio

    2012-07-01

    Full Text Available The one-pot synthesis of a Cu(II complex with partially oxidized tetrathiafulvalene (TTF moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF2] [CuICl2] was realized by the simultaneous occurrence of Cu(II complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.

  10. 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.

  11. 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.

  12. 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.

  13. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xiaoliang [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Liu, Peng [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); He, Hongping, E-mail: hehp@gig.ac.cn [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Wei, Gaoling [Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Chen, Tianhu [School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009 (China); Tan, Wei; Tan, Fuding [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China); Zhu, Jianxi; Zhu, Runliang [CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou 510640 (China)

    2016-04-05

    Highlights: • Calcination causes the activity variation of Mn-doped ferrites for HCHO oxidation. • The variation of catalytic activity of ferrites by calcination is non-linear. • Mn enriches on the calcinated ferrite surface in the valence of +3 and +4. • The reduction temperature of surface Mn{sup 4+} species is well correlated to T50. - Abstract: In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H{sub 2} temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200–600 °C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300–600 °C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400 °C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn{sup 4+} species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites.

  14. 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.

  15. The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation

    International Nuclear Information System (INIS)

    Liang, Xiaoliang; Liu, Peng; He, Hongping; Wei, Gaoling; Chen, Tianhu; Tan, Wei; Tan, Fuding; Zhu, Jianxi; Zhu, Runliang

    2016-01-01

    Highlights: • Calcination causes the activity variation of Mn-doped ferrites for HCHO oxidation. • The variation of catalytic activity of ferrites by calcination is non-linear. • Mn enriches on the calcinated ferrite surface in the valence of +3 and +4. • The reduction temperature of surface Mn"4"+ species is well correlated to T50. - Abstract: In this study, a series of Mn substituted spinel ferrites calcinated at different temperatures were used as catalysts for the oxidation of formaldehyde (HCHO). X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and H_2 temperature-programmed reduction were conducted to characterize the structure and physico-chemical properties of catalysts, which were affected by calcination in the range of 200–600 °C. Results show that all the ferrites were with spinel structure, and those calcinated in the range of 300–600 °C were in the phase of maghemite. The calcination changed the valence and distribution of Mn and Fe on the ferrite surface, and accordingly the reducibility of ferrites. The HCHO catalytic oxidation test showed that with the increase of calcination temperature, the activity was initially improved until 400 °C, but then decreased. The variation of HCHO conversion performance was well positively correlated to the variation of reduction temperature of surface Mn"4"+ species. The remarkable effect of calcination on the catalytic activity of Mn-doped spinel ferrites for HCHO oxidation was discussed in view of reaction mechanism and variations in cationic microstructure of Mn-doped ferrites.

  16. Understanding Catalytic Activity Trends for NO Decomposition and CO Oxidation using Density Functional Theory and Microkinetic Modeling

    DEFF Research Database (Denmark)

    Falsig, Hanne

    -metal surfaces by combining a database of adsorption energies on stepped metal surfaces with known Brønsted–Evans–Polanyi (BEP) relations for the activation barriers of dissociation of diatomic molecules over stepped transition- and noble-metal surfaces. The potential energy diagram directly points to why Pd......The main aim of this thesis is to understand the catalytic activity of transition metals and noble metals for the direct decomposition of NO and the oxidation of CO. The formation of NOx from combustion of fossil and renewable fuels continues to be a dominant environmental issue. We take one step...... towards rationalizing trends in catalytic activity of transition metal catalysts for NO decomposition by combining microkinetic modelling with density functional theory calculations. We establish the full potential energy diagram for the direct NO decomposition reaction over stepped transition...

  17. Effect of Composition and Mass Ratio on the Catalytic Wet Air Oxidation Catalyst Cu–Fe–La/FSC

    Directory of Open Access Journals (Sweden)

    Wu Chao

    2016-01-01

    Full Text Available The catalytic wet air oxidation (CWAO technology is used for the treatment of the simulated printing and dyeing wastewater and also for investigating the catalyst performance indicators such as catalyst activity and stability. The catalyst activity is mainly reflected from the water decolorization and CODCr removal rates, and the stability of the catalyst is mainly reflected by the quantity of metal dissolution. The experimental results showed that the prepared Cu–Fe–La/FSC catalyst with a 1:1:2 ratio of Cu–Fe–La by the impregnation method exhibited good activity for the treatment of the simulated printing and dyeing wastewater by the CWAO method, and the decolorization and CODCr removal rates using this catalyst were 98.7% and 78.6%, respectively, with a higher catalytic activity, lower concentration of metal dissolution, and good stability.

  18. A bioinspired catalytic aerobic oxidative C-H functionalization of primary aliphatic amines: synthesis of 1,2-disubstituted benzimidazoles.

    Science.gov (United States)

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-09-01

    Aerobic oxidative CH functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  19. Promotion of catalytic performance by adding W into Pt/ZrO{sub 2} catalyst for selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Mengmeng [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); Wang, Suning; Li, Yuanshan [College of Chemical Engineering, Sichuan University, Chengdu 610064, Sichuan (China); Xu, Haidi, E-mail: xuhaidi@scu.edu.cn [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); Chen, Yaoqiang, E-mail: nic7501@scu.edu.cn [Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610064, Sichuan (China); College of Chemical Engineering, Sichuan University, Chengdu 610064, Sichuan (China)

    2017-04-30

    Highlights: • The tungsten species weaken platinum-oxygen bond strength. • Pt{sup 0} was the active species of ammonia oxidation reaction in the low temperature. • Some PtO species could convert to Pt [111] beside WO{sub 3} species. - Abstract: Pt-WO{sub 3}/ZrO{sub 2} catalyst was prepared by co-impregnation method to improve the ammonia oxidation performance of Pt/ZrO{sub 2}. Differences in textural, structural, surface chemical states, redox properties and acid properties, together with the catalytic performance of Pt/ZrO{sub 2} and Pt-WO{sub 3}/ZrO{sub 2} catalysts were investigated systematically. The results of H{sub 2}-TPR revealed that higher reduction ability was possessed by Pt-WO{sub 3}/ZrO{sub 2} than that of Pt/ZrO{sub 2} due to the influence of tungsten on platinum. The XPS results showed that electron transfer from tungsten to platinum species made higher electron density around platinum. The TEM results revealed that the active lattice plane Pt[111] was obtained by modification of W species. Consequently, Pt-WO{sub 3}/ZrO{sub 2} exhibited obviously better ammonia oxidation performance compared with Pt/ZrO{sub 2}, the light-off temperature of NH{sub 3} shifted from 284 °C to 249 °C, the activation energy decreased from 113.4 kJ mol{sup −1} to 96.2 kJ mol{sup −1}.

  20. EFFECT OF IMPREGNATION PROCEDURE OF Pt/γ-Al2O3 CATALYSTS UPON CATALYTIC OXIDATION OF CO

    Directory of Open Access Journals (Sweden)

    Triyono Triyono

    2010-06-01

    Full Text Available The oxidation of carbon monoxide by oxygen using two catalysts prepared by two different methods has been investigated. In the first method, catalyst prepared by immersing γ-Al2O3 into the hexa-chloroplatinic acid solution at 80oC for 4 h, resulted Pt/γ-Al2O3 catalyst having platinum highly dispersed on the support. While that of immersing γ-Al2O3 in the hexa-chloroplatinic acid solution at room temperature for 12 h, produced Pt/ γ-Al2O3 catalyst where platinum dispersion was much lower. Catalytic activity test showed that platinum well dispersed on the support enhanced the activity of oxidation of carbon monoxide. The platinum impregnated at room temperature resulted in the poor activity.   Keyword: Catalyst, CO Oxidation, Platinum.

  1. High catalytic activity of ultrafine nanoporous palladium for electro-oxidation of methanol, ethanol, and formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiaoguang; Wang, Weimin; Qi, Zhen; Zhao, Changchun; Ji, Hong; Zhang, Zhonghua [Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (MOE), School of Materials Science and Engineering, Shandong University, Jingshi Road 73, Jinan 250061 (China)

    2009-10-15

    Nanoporous palladium (NPPd) with ultrafine ligament size of 3-6 nm was fabricated by dealloying of an Al-Pd alloy in an alkaline solution. Electrochemical measurements indicate that NPPd exhibits significantly high electrochemical active specific surface area (23 m{sup 2} g{sup -1}), and high catalytic activity for electro-oxidation of methanol, ethanol, and formic acid. Mass activities can reach 149, 148, 262 mA mg{sup -1} for the oxidation of methanol, ethanol and formic acid, respectively. Moreover, superior steady-state activities can be observed for all the electro-oxidation processes. NPPd will be a promising candidate for the anode catalyst for direct alcohol or formic acid fuel cells. (author)

  2. Co/Zr substitution in a cerium-zirconium oxide by catalytic steam reforming of bio-ethanol

    International Nuclear Information System (INIS)

    Vargas, J.C.; Thomas, S.; Roger, A.C.; Kiennemann, A.; Vargas, J.C.

    2006-01-01

    This work deals with the production of hydrogen by bio-ethanol catalytic steam reforming. The aim is to develop a catalyst active in ethanol conversion, selective in hydrogen and resistant to deactivation, particularly those induced by the formation of carbon deposition. The metal-support interaction being one of the keys of this challenge, catalysts in which a transition metal is inserted into an oxide by a liquid synthesis method (by the precursor method) have been developed. The initial insertion of cobalt into a cerium oxide-zirconia structure presents the advantages to increase the redox properties of the host oxide and to allow a stable reduction of a cobalt part while favoring the metal-support interaction. (O.M.)

  3. Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

    Science.gov (United States)

    Opila, Elizabeth J.; Boyd, Meredith

    2010-01-01

    SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

  4. 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

  5. Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

    International Nuclear Information System (INIS)

    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

  6. Synthesis of ZSM-5 zeolite from coal fly ash and rice husk: characterization and application for partial oxidation of methane to methanol

    Science.gov (United States)

    Krisnandi, Y. K.; Yanti, F. M.; Murti, S. D. S.

    2017-04-01

    Indonesian fly ash (SiO2/Al2O3 mole ratio = 3.59) was used together with rice husk (SiO2 92%) as raw material for mesoporous ZSM-5 zeolite synthesis. Prior being used, coal fly ash and rice husk were subjected to pre-treatment in order to extract silicate (SiO4 4-) and aluminate (AlO4 5-) and to remove the impurities. Then the ZSM-5 zeolite were synthesized through hydrothermal treatment using two types of templates (TPAOH and PDDA). The as-synthesized ZSM-5 was characterized using FTIR, XRD, SEM-EDX, and BET. The result of FTIR showed peaks at 1250-950 cm-1 (v asymetric T-O), 820-650 cm-1 (v symetric T-O), and at 650-500 cm-1 confirming the presence of the five number ring of the pentasil structure. The result of XRD showed the appearance of certain peaks in the position 2 theta between 7-9° and 22-25° indicative of ZSM-5 structure, but also showed the pattern of low intensity magnetite and hematite. The SEM image showed the rough surface of hexagonal crystals from ZSM-5 structure, indicative of mesoporosity in the structure. EDX result showed Si/Al ratio of 20, while surface area analysis gave SA of 43.16. The ZSM-5 zeolites then was modified with cobalt oxide through impregnation method. The catalytic activity as heterogeneous catalysts in partial oxidation of methane was tested. The result showed that hence the catalytic activity of ZSM-5 and Co/ZSM-5 from fly ash and rice husk were still inferior compared to the pro-analysis sourced-counterpart, they were potential to be used as catalyst in the partial oxidation of methane to methanol.

  7. Synthesis of acetic acid by catalytic oxidation of butenes-2. Synthesis of acetic acid from sec. -butyl alcohol and methyl ethyl ketone in vapor-phase catalytic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Yamashita, T.; Matsuzawa, Y.; Ninagawa, S.

    1977-11-01

    Eleven binary catalysts containing vanadium pentoxide (V/sub 2/O/sub 5/), 17 binary catalysts containing cobalt oxide (Co/sub 3/O/sub 4/), and 18 ternary catalysts containing both V/sub 2/O/sub 5/ and Co/sub 3/O/sub 4/ were screened for the stepwise conversion of sec.-butanol to methyl ethyl ketone (MEK) and acetic acid. Of the binary catalysts, 4:1 Rh/V and Co/V binary oxides gave the best acetic acid yields. With the Co/V catalyst, the selectivity for MEK increased rapidly as the cobalt content of the catalyst increased above 50%, reaching 81% at 226/sup 0/C and 90% conversion on 9:1 Co/V oxide. The 9:1 Co/V catalyst also yielded acetaldehyde from ethanol with 98% selectivity at 210/sup 0/C and acetone from isopropanol with 98% selectivity at 200/sup 0/C, but dehydrated tert.-butanol to isobutene. V/Cr and V/Sb binary oxides were the most effective catalysts for the oxidation of MEK to acetic acid, with 78-88% selectivities at 100% conversion at 260/sup 0/C. Of the ternary oxides tested for the one-step conversion of sec.-butanol to acetic acid, a 6:2:2 Co/V/Al catalyst gave best results, (i.e., 34% selectivity for acetic acid (45% for total acids) at 100% conversion and 68% selectivity (90% for total acids) at 50Vertical Bar3< conversion). Graphs, tables, and 21 references.

  8. 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.

  9. 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.

  10. Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

    Science.gov (United States)

    Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

    2017-07-01

    We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

  11. Synthesis and application of multiple rods gold-zinc oxide nano structures in the photo catalytic degradation of methyl orange

    International Nuclear Information System (INIS)

    Arab Chamjangali, M.; Bagherian, G.; Bahramian, B.; Fahimi Rad, B.

    2015-01-01

    Zinc oxide and gold-zinc oxide (Au-Zn O) nano structures with multiple rods (multi pods) morphology were successfully prepared. Au-Zn O nano structures were synthesized via a simple precipitation route method in the presence of oligo aniline-coated gold nanoparticles. The Au-Zn O catalyst obtained was applied for the degradation of methyl orange in an aqueous solution under UV irradiation Effects of the operational parameters such as the solution p H, amount of photocatalyst, and dye concentration on the photo catalytic degradation and decolorisation of methyl orange were studied. Detailed studies including kinetic study and regeneration of catalyst were carried out on the optimal conditions for the photodegradation of methyl orange by Au-Zn O multi pods in aqueous solution. Effect of foreign species on the photodegradation of methyl orange was also studied. An enhancement of the photo catalytic activities for photodegradation of methyl orange was observed when the gold nanoparticles were loaded on the zinc oxide multi pods. The proposed catalyst was applied for the degradation of methyl orange in synthetic wastewater samples with satisfactory results.

  12. 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.

  13. Partial oxidation of methane over Ni/Mg/Al/La mixed oxides prepared from layered double hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jun [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Zhao, Ning; Wei, Wei [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Sun, Yuhan [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China)

    2010-11-15

    A series of Ni/Mg/Al/La mixed oxides prepared by thermal decomposition of layered double hydrotalcites (HT) were characterized by XRD, ICP, EXAFS, TGA, TPR-H{sub 2}, SEM, and N{sub 2} adsorption/desorption technique. The results revealed the formation of periclase-type catalysts with mesoporous structure, and the addition of La{sup 3+} lowered the phase crystallization with the formation of small oxide particles. Such catalysts had both high activities and stabilities toward partial oxidation of methane (POM). The catalyst containing 6.5 mol.% La{sup 3+} showed the highest performance at 1053 K with CH{sub 4} conversion of 99%, CO selectivity of 93% and H{sub 2} selectivity of 96%, which could be attributed to the presence of highly dispersed nickel and then the resistance to coke formation due to the promotion effect of lanthanum. (author)

  14. Determination of molybdenum (VI) by its catalytic effect on the oxidation of nile blue by hydrogen peroxide

    International Nuclear Information System (INIS)

    Ensafi, Ali A.; Sadeghie, Majid M.; Alaie-Yazdie, F.

    1998-01-01

    A spectrophotometric reaction rate method for the determination of molybdenum is described, based on its catalytic effect on the oxidation of nile blue by hydrogen peroxide. The decrease in absorbance of nile blue with time from 0.5 to 4 min at 590 nm is proportional to the concentration of Mo(VI) over the range 0.022-1000 μg/ml. The limit of detection of molybdenum(VI) is 0.008 μg/ml. The precision and the effect of more than forty ions are reported. The procedure has been successfully applied for the determination of molybdenum (VI) in plant materials and steel samples. (author)

  15. 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....

  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. 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...

  18. 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

  19. 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.

  20. Catalytic oxidation of sulfide in drinking water treatment: activated carbon as catalyst; Katalytische Oxidation von Sulfid bei der Trinkwasseraufbereitung: Aktivkohle als Katalysator

    Energy Technology Data Exchange (ETDEWEB)

    Hultsch, V; Grischek, T; Wolff, D; Worch, E [Technische Univ. Dresden (Germany). Inst. fuer Wasserchemie; Gun, J [Hebrew Univ. of Jerusalem (Israel). Div. of Environmental Sciences, Fredy and Nadine Herrmann School of Applied Science

    2001-07-01

    In regions with warm climate and limited water resources high sulfide concentrations in groundwater can cause problems during drinking water treatment. Aeration of the raw water is not always sufficient to ensure the hydrogen sulfide concentration below the odour threshold value for hydrogen sulfide. As an alternative, activated carbon can be used as a catalyst for sulfide oxidation of raw water. The use of different types of activated carbon was investigated in kinetic experiments. Both Catalytic Carbon from Calgon Carbon and granulated activated carbon from Norit showed high catalytic activities. The results of the experiments are discussed with regard to the practical use of activated carbon for the elimination of hydrogen sulfide during drinking water treatment. (orig.)

  1. Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils.

    Science.gov (United States)

    Ward, Collin P; Cory, Rose M

    2016-04-05

    Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

  2. 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.

  3. 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.

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

    Science.gov (United States)

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

    2011-02-01

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

  5. 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.

  6. 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

  7. Oxidative cracking of n-hexane: a catalytic pathway to olefins

    NARCIS (Netherlands)

    Boyadjian, C.A.

    2010-01-01

    Steam cracking, the major, current existing route for light olefin production, is the most energy consuming process in the chemical industry. The need for an energy efficient processes, urged substantial research work for the development of new catalytic technologies for light olefin production.

  8. Catalytic oxidation of o-aminophenols and aromatic amines by mushroom tyrosinase.

    Science.gov (United States)

    Muñoz-Muñoz, Jose Luis; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon; Tudela, Jose; Rodriguez-Lopez, Jose N; Garcia-Canovas, Francisco

    2011-12-01

    The kinetics of tyrosinase acting on o-aminophenols and aromatic amines as substrates was studied. The catalytic constants of aromatic monoamines and o-diamines were both low, these results are consistent with our previous mechanism in which the slow step is the transfer of a proton by a hydroxyl to the peroxide in oxy-tyrosinase (Fenoll et al., Biochem. J. 380 (2004) 643-650). In the case of o-aminophenols, the hydroxyl group indirectly cooperates in the transfer of the proton and consequently the catalytic constants in the action of tyrosinase on these compounds are higher. In the case of aromatic monoamines, the Michaelis constants are of the same order of magnitude than for monophenols, which suggests that the monophenols bind better (higher binding constant) to the enzyme to facilitate the π-π interactions between the aromatic ring and a possible histidine of the active site. In the case of aromatic o-diamines, both the catalytic and Michaelis constants are low, the values of the catalytic constants being lower than those of the corresponding o-diphenols. The values of the Michaelis constants of the aromatic o-diamines are slightly lower than those of their corresponding o-diphenols, confirming that the aromatic o-diamines bind less well (lower binding constant) to the enzyme. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Modifications induced by potassium addition on chromia/alumina catalysts and their influence on the catalytic activity for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Rombi, E.; Gazzoli, D.; Cutrufello, M.G.; De Rossi, S.; Ferino, I.

    2010-01-01

    The oxidative dehydrogenation of propane was investigated on K-containing chromia/alumina catalysts, with nominal Cr and K loadings of 10 and 0-2 wt%, respectively. Their chemical composition, structure, texture, nature of surface species, redox features and surface acidity were determined. Catalytic behaviour was investigated in a continuous-flow micro-reactor under different conditions. Besides the nature and concentration of the chromium species, potassium addition was found to affect the reducibility of the catalysts as well as their acid surface features. Such modifications were found to condition the catalytic behaviour, which appeared somewhat peculiar in comparison with that of the catalytic systems reported in literature.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Synthesis of Ru nanoparticles confined in magnesium oxide-modified mesoporous alumina and their enhanced catalytic performance during ammonia decomposition

    KAUST Repository

    Tan, Hua; Li, Kun; Sioud, Salim; Cha, Dong Kyu; Amad, Maan H.; Hedhili, Mohamed N.; Al-Talla, Zeyad

    2012-01-01

    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.

  15. Green approach for preparation of reduced graphene oxide decorated with gold nanoparticles and its optical and catalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Šimšíková, M., E-mail: michaela.simsikova@ceitec.vutbr.cz [CEITEC BUT, Brno University of Technology, Technická 10, 616 69 Brno (Czech Republic); Bartoš, M. [CEITEC BUT, Brno University of Technology, Technická 10, 616 69 Brno (Czech Republic); Institute of Physical Engineering, Brno University of Technology, Technická 2, 616 69 Brno (Czech Republic); Keša, P. [Department of Biochemistry, Faculty of Science, P.J. Šafárik University, Šrobárova 2, 041 54 Košice (Slovakia); Department of Biophysics, Institute of Experimental Physics, SAS, Watsonova 47, 040 01 Košice (Slovakia); Šikola, T. [CEITEC BUT, Brno University of Technology, Technická 10, 616 69 Brno (Czech Republic); Institute of Physical Engineering, Brno University of Technology, Technická 2, 616 69 Brno (Czech Republic)

    2016-07-01

    Graphene oxide (GO) was reduced and modified by gold nanoparticles using aqueous leaf extract of green tea. Successful formation of gold nanoparticles (AuNPs) on graphene oxide surface was determined by scanning electron microscopy (SEM). Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared analyses (FT-IR) have been used to demonstrate the behavior of complex of reduced graphene oxide with gold nanoparticles (rGO-AuNPs), the removal of oxygen-containing groups from the graphene, and subsequent formation of reduced graphene oxide (rGO). We also demonstrated the change of optical properties of GO after the reduction and formation of gold nanoparticles on its surface by UV–vis spectroscopy and fluorescence spectroscopy. The positive impact of rGO-AuNPs composite on safranin T reduction in the presence of NaBH{sub 4} without light irradiation was examined, as well. The dye decolorization was observed within 60 min which highlights the exceptional catalytic potential of the rGO-AuNPs. - Highlights: • Reduction of GO was performed by an environmentally friendly approach. • Gold nanoparticles were prepared by self-assembly on the graphene oxide surface. • Surface properties were enhanced after the formation of gold nanoparticles. • Optical properties have been changed after the graphene reduction and formation of gold nanoparticles. • The decolorization of safranin T was observed within 60 min.

  16. Green approach for preparation of reduced graphene oxide decorated with gold nanoparticles and its optical and catalytic properties

    International Nuclear Information System (INIS)

    Šimšíková, M.; Bartoš, M.; Keša, P.; Šikola, T.

    2016-01-01

    Graphene oxide (GO) was reduced and modified by gold nanoparticles using aqueous leaf extract of green tea. Successful formation of gold nanoparticles (AuNPs) on graphene oxide surface was determined by scanning electron microscopy (SEM). Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared analyses (FT-IR) have been used to demonstrate the behavior of complex of reduced graphene oxide with gold nanoparticles (rGO-AuNPs), the removal of oxygen-containing groups from the graphene, and subsequent formation of reduced graphene oxide (rGO). We also demonstrated the change of optical properties of GO after the reduction and formation of gold nanoparticles on its surface by UV–vis spectroscopy and fluorescence spectroscopy. The positive impact of rGO-AuNPs composite on safranin T reduction in the presence of NaBH_4 without light irradiation was examined, as well. The dye decolorization was observed within 60 min which highlights the exceptional catalytic potential of the rGO-AuNPs. - Highlights: • Reduction of GO was performed by an environmentally friendly approach. • Gold nanoparticles were prepared by self-assembly on the graphene oxide surface. • Surface properties were enhanced after the formation of gold nanoparticles. • Optical properties have been changed after the graphene reduction and formation of gold nanoparticles. • The decolorization of safranin T was observed within 60 min.

  17. One-pot synthesis of reduced graphene oxide supported PtCuy catalysts with enhanced electro-catalytic activity for the methanol oxidation reaction

    International Nuclear Information System (INIS)

    Peng, Xinglan; Zhao, Yanchun; Chen, Duhong; Fan, Yanfang; Wang, Xiao; Wang, Weili; Tian, Jianniao

    2014-01-01

    The outstanding performance PtCu y (y = 1,2,3) alloy nanoparticles supported on reduced graphene oxide (rGO) have been synthesized by a facile, efficient, one-pot hydrothermal synthesis approach. The as-prepared PtCu y /rGO catalysts are comprehensively characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy. Cyclic voltammetry, CO-stripping voltammetry and chronoamperometry results reveal that the PtCu y /rGO catalysts have higher electro-catalytic activity, more negative onset oxidative potential, more excellent tolerance ability for CO poisoning and enhanced stability for the electro-oxidation of methanol compared to pure Pt/rGO. As far as the as-made PtCu y /rGO catalysts are concerned, the PtCu 2 /rGO exhibits the highest electro-catalytic activity. The mechanism of the promoting effect of Cu on Pt is explained based on the electronic modification effect. The nature of interfacial interactions between the Pt-Cu active metal phase and the rGO supporting materials is crucial to achieving high performance

  18. 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.

  19. 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.

  20. Catalytic wet air oxidation of coke-plant wastewater on ruthenium-based eggshell catalysts in a bubbling bed reactor.

    Science.gov (United States)

    Yang, M; Sun, Y; Xu, A H; Lu, X Y; Du, H Z; Sun, C L; Li, C

    2007-07-01

    Catalytic wet air of coke-plant wastewater was studied in a bubbling bed reactor. Two types of supported Ru-based catalysts, eggshell and uniform catalysts, were employed. Compared with the results in the wet air oxidation of coke-plant wastewater, supported Ru uniform catalysts showed high activity for chemical oxygen demand (COD) and ammonia/ammonium compounds (NH3-N) removal at temperature of 250 degrees C and pressure of 4.8 MPa, and it has been demonstrated that the catalytic activity of uniform catalyst depended strongly on the distribution of active sites of Ru on catalyst. Compared to the corresponding uniform catalysts with the same Ru loading (0.25 wt.% and 0.1 wt.%, respectively), the eggshell catalysts showed higher activities for CODcr removal and much higher activities for NH3-N degradation. The high activity of eggshell catalyst for treatment of coke-plant wastewater can be attributed to the higher density of active Ru sites in the shell layer than that of the corresponding uniform catalyst with the same Ru loading. It has been also evidenced that the active Ru sites in the internal core of uniform catalyst have very little or no contribution to CODcr and NH3-N removal in the total oxidation of coke-plant wastewater.

  1. 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.

  2. 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...

  3. 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.

  4. Reactivity of organic compounds in catalytic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Minachev, Kh M; Bragin, O V

    1978-01-01

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

  5. Catalytic Oxidation of CO and Soot over Ce-Zr-Pr Mixed Oxides Synthesized in a Multi-Inlet Vortex Reactor: Effect of Structural Defects on the Catalytic Activity.

    Science.gov (United States)

    Bensaid, Samir; Piumetti, Marco; Novara, Chiara; Giorgis, Fabrizio; Chiodoni, Angelica; Russo, Nunzio; Fino, Debora

    2016-12-01

    In the present work, ceria, ceria-zirconia (Ce = 80 at.%, Zr = 20 at.%), ceria praseodymia (Ce = 80 at.%, Pr = 20 at.%) and ceria-zirconia-praseodymia catalysts (Ce = 80 at.%, Zr = 10 at.% and Pr = 10 at.%) have been prepared by the multi-inlet vortex reactor (MIVR). For each set of samples, two inlet flow rates have been used during the synthesis (namely, 2 ml min -1 , and 20 ml min -1 ) in order to obtain different particle sizes. Catalytic activity of the prepared materials has been investigated for CO and soot oxidation reactions. As a result, when the catalysts exhibit similar crystallite sizes (in the 7.7-8.8 nm range), it is possible to observe a direct correlation between the O v /F 2g vibrational band intensity ratios and the catalytic performance for the CO oxidation. This means that structural (superficial) defects play a key role for this process. The incorporation of Zr and Pr species into the ceria lattice increases the population of structural defects, as measured by Raman spectroscopy, according to the order: CeO 2  oxidation activity for these catalysts, in contrast with nanostructured ones (e.g., Ce-Zr-O nanopolyhedra, Ce-Pr-O nanocubes) described elsewhere (Andana et al. Appl. Catal. B 197: 125-137, 2016; Piumetti et al., Appl Catal B 180: 271-282, 2016).

  6. Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films

    KAUST Repository

    Sun, Ke; Saadi, Fadl H.; Lichterman, Michael F.; Hale, William G.; Wang, Hsinping; Zhou, Xinghao; Plymale, Noah T.; Omelchenko, Stefan T.; He, Jr-Hau; Papadantonakis, Kimberly M.; Brunschwig, Bruce S.; Lewis, Nathan S.

    2015-01-01

    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

  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. Amorphous saturated Cerium-Tungsten-Titanium oxide nanofibers catalysts for NOx selective catalytic reaction

    DEFF Research Database (Denmark)

    Dankeaw, Apiwat; Gualandris, Fabrizio; Silva, Rafael Hubert

    2018-01-01

    experiments at the best working conditions (dry and in absence of SO2) are performed to characterize the intrinsic catalytic behavior of the new catalysts. At temeprature lower than 300 °C, superior NOx conversion properties of the amorphous TiOx nanofibers over the crystallized TiO2 (anatase) nanofibers......Herein for the first time, Ce0.184W0.07Ti0.748O2-δ nanofibers are prepared by electrospinning to serve as catalyst in the selective catalytic reduction (SCR) process. The addition of cerium is proven to inhibit crystallization of TiO2, yielding an amorphous TiOx-based solid solution stable up...... temperatures (catalysts in a wide range...

  10. 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

  11. 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

  12. Synthesis of ternary oxide for efficient photo catalytic conversion of CO2

    Science.gov (United States)

    Wan, Lijuan

    2018-01-01

    Zn2GeO4 Nan rods were prepared by solution phase route. The morphology and structure of the as-prepared products were characterized by scanning electron microscopy (SEM) and Bruner-Emmett-Teller (BET) surface area measurements. The results revealed that Zn2GeO4 Nan rods with higher surface area have higher photo catalytic activity in photo reduction of CO2 than Zn2GeO4 prepared through solid-state reaction.

  13. Catalytic properties of oxygen adsorbed on NiO-Sm/sub 2/O/sub 3/ binary oxides

    Energy Technology Data Exchange (ETDEWEB)

    Tadasu, Y.; Niwa, H.; Matsuda, Y.

    1978-02-01

    Various rare earths were screened as promoters for a nickel oxidation catalyst, and samarium (Sm) was selected for further studies. The activity of a physical mixture of NiO/Sm/sub 2/O/sub 3/ and SiC for the oxidation of 500 ppm nitric oxide with 5% oxygen in nitrogen to nitrogen dioxide at 320/sup 0/C went through a maximum with increasing Sm/sub 2/O/sub 3/ content of the catalyst. The most active catalyst, which contained 3.75% Sm/sub 2/O/sub 3/, was 3.7 times as active as pure nickel oxide. Temperature-programed desorption of oxygen from the catalysts revealed three peaks, ..cap alpha.. at 220/sup 0/-230/sup 0/C ..beta.. at 370/sup 0/-380/sup 0/C, and ..gamma.. at 530/sup 0/-540/sup 0/C, for all catalysts except pure Sm/sub 2/O/sub 3/. The amount of adsorbed oxygen increased with increasing Sm/sub 2/O/sub 3/ content to 3.75%, and then decreased with further Sm/sub 2/O/sub 3/ increases. The catalytic activity was correlated to oxygen in the ..beta..-state. Graphs, spectra, and table.

  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. Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

    Science.gov (United States)

    Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

    2014-12-01

    Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

  16. 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.

  17. Role of Defects and Adsorbed Water Film in Influencing the Electrical, Optical and Catalytic Properties of Transition Metal Oxides

    Science.gov (United States)

    Wang, Qi

    Transition metal oxides (TMOs) constitute a large group of materials that exhibit a wide range of optical, electrical, electrochemical, dielectric and catalytic properties, and thus making them highly regarded as promising materials for a variety of applications in next generation electronic, optoelectronic, catalytic, photonic, energy storage and energy conversion devices. Some of the unique properties of TMOs are their strong electron-electron correlations that exists between the valence electrons of narrow d- or f-shells and their ability to exist in variety of oxidation states. This gives TMOs an enormous range of fascinating electronic and other physical properties. Many of these remarkable properties of TMOs arises from the complex surface charge transfer processes at the oxide surface/electrochemical redox species interface and non-stoichiometry due to the presence of lattice vacancies that may cause significant perturbation to the electronic structure of the material. Stoichiometry, oxidation state of the metal center and lattice vacancy defects all play important roles in affecting the physical properties, electronic structures, device behavior and other functional properties of TMOs. However, the underlying relationships between them is not clearly known. For instance, the exchange of electrons between adsorbates and defects can lead to the passivation of existing defect states or formation of new defects, both of which affect defect equilibria, and consequently, functional properties. In depth understanding of the role of lattice defects on the electrical, catalytic and optical properties of TMOs is central to further expansion of the technological applications of TMO based devices. The focus of this work is to elucidate the interactions of vacancy defects with various electrochemical adsorbates in TMOs. The ability to directly probe the interactions of vacancy defects with gas and liquid phase species under in-operando conditions is highly desirable to

  18. Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

    2016-02-28

    Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

  19. 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.

  20. Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

    Science.gov (United States)

    Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

    2014-02-03

    A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

  1. Comparison of Efficiencies and Mechanisms of Catalytic Ozonation of Recalcitrant Petroleum Refinery Wastewater by Ce, Mg, and Ce-Mg Oxides Loaded Al2O3

    Directory of Open Access Journals (Sweden)

    Chunmao Chen

    2017-02-01

    Full Text Available The use of catalytic ozonation processes (COPs for the advanced treatment of recalcitrant petroleum refinery wastewater (RPRW is rapidly expanding. In this study, magnesium (Mg, cerium (Ce, and Mg-Ce oxide-loaded alumina (Al2O3 were developed as cost efficient catalysts for ozonation treatment of RPRW, having performance metrics that meet new discharge standards. Interactions between the metal oxides and the Al2O3 support influence the catalytic properties, as well as the efficiency and mechanism. Mg-Ce/Al2O3 (Mg-Ce/Al2O3-COP reduced the chemical oxygen demand by 4.7%, 4.1%, 6.0%, and 17.5% relative to Mg/Al2O3-COP, Ce/Al2O3-COP, Al2O3-COP, and single ozonation, respectively. The loaded composite metal oxides significantly increased the hydroxyl radical-mediated oxidation. Surface hydroxyl groups (–OHs are the dominant catalytic active sites on Al2O3. These active surface –OHs along with the deposited metal oxides (Mg2+ and/or Ce4+ increased the catalytic activity. The Mg-Ce/Al2O3 catalyst can be economically produced, has high efficiency, and is stable under acidic and alkaline conditions.

  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. Heterogeneous catalytic ozonation of biologically pretreated Lurgi coal gasification wastewater using sewage sludge based activated carbon supported manganese and ferric oxides as catalysts.

    Science.gov (United States)

    Zhuang, Haifeng; Han, Hongjun; Hou, Baolin; Jia, Shengyong; Zhao, Qian

    2014-08-01

    Sewage sludge of biological wastewater treatment plant was converted into sewage sludge based activated carbon (SBAC) with ZnCl₂ as activation agent, which supported manganese and ferric oxides as catalysts (including SBAC) to improve the performance of ozonation of real biologically pretreated Lurgi coal gasification wastewater. The results indicated catalytic ozonation with the prepared catalysts significantly enhanced performance of pollutants removal and the treated wastewater was more biodegradable and less toxic than that in ozonation alone. On the basis of positive effect of higher pH and significant inhibition of radical scavengers in catalytic ozonation, it was deduced that the enhancement of catalytic activity was responsible for generating hydroxyl radicals and the possible reaction pathway was proposed. Moreover, the prepared catalysts showed superior stability and most of toxic and refractory compounds were eliminated at successive catalytic ozonation runs. Thus, the process with economical, efficient and sustainable advantages was beneficial to engineering application. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Effects of Oxygen Partial Pressure on Oxidation Behavior of CMnSi TRIP Steel in an Oxidation-Reduction Scheme

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong-Hwan; Huh, Joo-Youl [Korea University, Seoul (Korea, Republic of); Kim, Myung-Soo; Kim, Jong-Sang [POSCO Technical Research Laboratories, Gwangyang (Korea, Republic of)

    2017-02-15

    An oxidation-reduction scheme is an alternative approach for improving the galvanizability of advanced high-strength steel in the continuous hot-dip galvanizing process. Here, we investigated the effect of oxygen partial pressure (Po{sub 2}) on the oxidation behavior of a transformation-induced plasticity steel containing 1.5 wt% Si and 1.6 wt% Mn during heating to and holding for 60 s at 700 ℃ under atmospheres with various Po{sub 2} values. Irrespective of Po{sub 2}, a thin amorphous Si-rich layer of Si-Mn-O was formed underneath the Fe oxide scale (a Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} bilayer) in the heating stage. In contrast to Si, Mn tended to segregate at the scale surface as (Fe,Mn){sub 2}O{sub 3}. The multilayered structure of (Fe,Mn){sub 2}O{sub 3}/Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4}/amorphous Si-Mn-O remained even after extended oxidizing at 700 ℃ for 60 s. Fe{sub 2}O{sub 3} was the dominantly growing oxide phase in the scale. The enhanced growth rate of Fe{sub 2}O{sub 3} with increasing Po{sub 2} resulted in the formation of more Kirkendall voids in the amorphous Si-rich layer and a less Mn segregation at the scale surface. The mechanisms underlying the absence of FeO and the formation of Kirkendall voids are discussed.

  6. 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.

  7. Nitrous Oxide Production in a Granule-based Partial Nitritation Reactor: A Model-based Evaluation.

    Science.gov (United States)

    Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

    2017-04-03

    Sustainable wastewater treatment has been attracting increasing attentions over the past decades. However, the production of nitrous oxide (N 2 O), a potent GHG, from the energy-efficient granule-based autotrophic nitrogen removal is largely unknown. This study applied a previously established N 2 O model, which incorporated two N 2 O production pathways by ammonia-oxidizing bacteria (AOB) (AOB denitrification and the hydroxylamine (NH 2 OH) oxidation). The two-pathway model was used to describe N 2 O production from a granule-based partial nitritation (PN) reactor and provide insights into the N 2 O distribution inside granules. The model was evaluated by comparing simulation results with N 2 O monitoring profiles as well as isotopic measurement data from the PN reactor. The model demonstrated its good predictive ability against N 2 O dynamics and provided useful information about the shift of N 2 O production pathways inside granules for the first time. The simulation results indicated that the increase of oxygen concentration and granule size would significantly enhance N 2 O production. The results further revealed a linear relationship between N 2 O production and ammonia oxidation rate (AOR) (R 2  = 0.99) under the conditions of varying oxygen levels and granule diameters, suggesting that bulk oxygen and granule size may exert an indirect effect on N 2 O production by causing a change in AOR.

  8. Partial oxidation of municipal sludge with activited carbon catalyst in supercritical water

    International Nuclear Information System (INIS)

    Guo Yang; Wang Shuzhong; Gong Yanmeng; Xu Donghai; Tang Xingying; Ma Honghe

    2010-01-01

    The partial oxidation (POX) characteristics of municipal sludge in supercritical water (SCW) were investigated by using batch reactor. Effects of reaction parameters such as oxidant equivalent ratio (OER), reaction time and temperature were investigated. Activated carbon (AC) could effectively improve the mole fraction of H 2 in gas product at low OER. However, high OER (greater than 0.3) not only led to the combustion reaction of CO and H 2 , but also caused corrosion of reactor inner wall. Hydrogenation and polymerization of the intermediate products are possible reasons for the relative low COD removal rate in our tests. Metal oxide leached from the reactor inner wall and the main components of the granular sludge were deposited in the AC catalyst. Reaction time had more significant effect on BET surface area of AC than OER had. Long reaction time led to the methanation reaction following hydrolysis and oxidation reaction of AC in SCW in the presence of oxygen. Correspondingly, the possible reaction mechanisms were proposed.

  9. Hydrogen cyanide formation in selective catalytic reduction of nitrogen oxides over Cu/ZSM-5

    Energy Technology Data Exchange (ETDEWEB)

    Radtke, F; Koeppel, R; Baiker, A [Department of Chemical Engineering and Industrial Chemistry, Swiss Federal Institute of Technology, Zurich, (Switzerland)

    1994-01-06

    Hydrogen cyanide is formed over Cu/ZSM-5 during the selective catalytic reduction of NO[sub x] by either propylene or ethylene in the temperature range 450-600 K. Under the reaction conditions used (reactant feed: 973 ppm NO, 907 ppm propene or 1448 ppm ethylene, 2% oxygen, W/F=0.1 g s cm[sup -3]), the concentration of hydrogen cyanide reaches 20, respectively, 30 ppm, depending on whether ethylene or propene are used as hydrocarbons. In addition, significant N[sub 2]O formation is observed at temperatures lower than 700 K, independent of the hydrocarbon used

  10. 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.

  11. 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.

  12. Influence of chirality on catalytic generation of nitric oxide and platelet behavior on selenocystine immobilized TiO2 films.

    Science.gov (United States)

    Fan, Yonghong; Pan, Xiaxin; Wang, Ke; Wu, Sisi; Han, Honghong; Yang, Ping; Luo, Rifang; Wang, Hong; Huang, Nan; T