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Sample records for selective catalytic oxidations

  1. 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.)

  2. 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.)

  3. 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.)

  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.). 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.

  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. 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.

  7. 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...

  8. 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.

  9. 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...

  10. 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.)

  11. 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)

  12. 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.

  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. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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...

  6. 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

  7. 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.

  8. Catalytic performance of advanced titanosilicate selective oxidation catalysts – a review

    Czech Academy of Sciences Publication Activity Database

    Přech, Jan

    2017-01-01

    Roč. 60, č. 1 (2017), s. 71-131 ISSN 0161-4940 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Epoxidation * hydrogen peroxide * selective oxidation * titanosilicate * zeolite Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 6.143, year: 2016

  9. Kinetic studies of electrochemical generation of Ag(II) ion and catalytic oxidation of selected organics

    International Nuclear Information System (INIS)

    Zawodzinski, C.; Smith, W.H.; Martinez, K.R.

    1993-01-01

    The goal of this research is to develop a method to treat mixed hazardous wastes containing selected organic compounds and heavy metals, including actinide elements. One approach is to destroy the organic via electrochemical oxidation to carbon dioxide, then recover the metal contaminants through normally accepted procedures such as ion exchange, precipitation, etc. The authors have chosen to study the electrochemical oxidation of a simple alcohol, iso-propanol. Much of the recent work reported involved the use of an electron transfer mediator, usually the silver(I)/(II) redox couple. This involved direct electrochemical generation of the mediator at the anode of a divided cell followed by homogeneous reaction of the mediator with the organic compound. In this study the authors have sought to compare the mediated reaction with direct electrochemical oxidation of the organic. In addition to silver(I)/(II) they also looked at the cobalt(II)/(III) redox coupled. In the higher oxidation state both of these metal ions readily hydrolyze in aqueous solution to ultimately form insoluble oxide. The study concluded that in a 6M nitric acid solution at room temperature iso-propanol can be oxidized to carbon dioxide and acetic acid. Acetic acid is a stable intermediate and resists further oxidation. The presence of Co(III) enhances the rate or efficiency of the reaction

  10. 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

  11. 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)

  12. Synthesis, Characterization and Catalytic Performance in the Selective Oxidation of Alcohols by Metallophthalocyanines Supported on Zinc Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Amin Ebadi

    2017-01-01

    Full Text Available Unsubstituted phthalocyanines of Co, Fe and Mn supported on zinc oxide nanoparticles were prepared and were well characterized with X-ray diffraction and scanning electron microscopy. The oxidation of alcohols with tert-butylhydroperoxide, in the presence of metallophthalocyanines supported on zinc oxide nanoparticles was investigated. These MPc/ZnO nanocomposites were effective catalysts for the oxidation of alcohols such as cyclohexanol (83.4% conversion; 100% selectivity, benzyl alcohol (70.5% conversion; 100% selectivity and hexanol (62.3% conversion; 100% selectivity. The influences of reaction time, various metals and type of substrates and oxidants on the oxidation of alcohols were also studied, and optimized conditions were investigated. Under these reaction conditions, the activity of the catalysts decreases in the following order:  CoPc/nano-ZnO > FePc/nano-ZnO > MnPc/nano-ZnO. It shows that TBHP is more efficient oxidant due to weaker O-O bond with respect to H2O2 and the following order has been observed for the percentage of conversions of alcohols: 2º > benzylic > 1º.

  13. 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

  14. Mercury Oxidation over Selective Catalytic Reduction (SCR) Catalysts - Ph.d. thesis Karin Madsen

    DEFF Research Database (Denmark)

    Madsen, Karin

    The vanadium-based SCR catalyst used for NOx-control promotes the oxidation of elemental mercury Hg0 to Hg2+ in flue gases from coal-fired power plants. Hg2+ is water soluble and can effectively be captured in a wet scrubber. This means that the combination of an SCR with a wet FGD can offer an e...

  15. Copper/ascorbic acid dyad as a catalytic system for selective aerobic oxidation of amines

    Czech Academy of Sciences Publication Activity Database

    Šrogl, Jiří; Voltrová, Svatava

    2009-01-01

    Roč. 11, č. 4 (2009), s. 843-845 ISSN 1523-7060 Institutional research plan: CEZ:AV0Z40550506 Keywords : copper * ascorbic acid * oxidative deamination Subject RIV: CC - Organic Chemistry Impact factor: 5.420, year: 2009

  16. 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.

  17. Gas Selectivity Control in Co3O4 Sensor via Concurrent Tuning of Gas Reforming and Gas Filtering using Nanoscale Hetero-Overlayer of Catalytic Oxides.

    Science.gov (United States)

    Jeong, Hyun-Mook; Jeong, Seong-Yong; Kim, Jae-Hyeok; Kim, Bo-Young; Kim, Jun-Sik; Abdel-Hady, Faissal; Wazzan, Abdulaziz A; Al-Turaif, Hamad Ali; Jang, Ho Won; Lee, Jong-Heun

    2017-11-29

    Co 3 O 4 sensors with a nanoscale TiO 2 or SnO 2 catalytic overlayer were prepared by screen-printing of Co 3 O 4 yolk-shell spheres and subsequent e-beam evaporation of TiO 2 and SnO 2 . The Co 3 O 4 sensors with 5 nm thick TiO 2 and SnO 2 overlayers showed high responses (resistance ratios) to 5 ppm xylene (14.5 and 28.8) and toluene (11.7 and 16.2) at 250 °C with negligible responses to interference gases such as ethanol, HCHO, CO, and benzene. In contrast, the pure Co 3 O 4 sensor did not show remarkable selectivity toward any specific gas. The response and selectivity to methylbenzenes and ethanol could be systematically controlled by selecting the catalytic overlayer material, varying the overlayer thickness, and tuning the sensing temperature. The significant enhancement of the selectivity for xylene and toluene was attributed to the reforming of less reactive methylbenzenes into more reactive and smaller species and oxidative filtering of other interference gases, including ubiquitous ethanol. The concurrent control of the gas reforming and oxidative filtering processes using a nanoscale overlayer of catalytic oxides provides a new, general, and powerful tool for designing highly selective and sensitive oxide semiconductor gas sensors.

  18. 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.

  19. A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

    Energy Technology Data Exchange (ETDEWEB)

    Rezaei, Behzad [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-84111 (Iran, Islamic Republic of)], E-mail: rezaei@cc.iut.ac.ir; Keyvanfard, Mohsen [Faculty of Science, Majlesi Campus, Islamic Azad University, Isfahan (Iran, Islamic Republic of)

    2008-03-01

    In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at {lambda}{sub max} = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL ({delta}A = 0.2819C{sub Ru} + 1.1840) and 20.0-100.0 ng/mL ({delta}A = 0.0984C{sub Ru} + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 {+-} 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples.

  20. A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

    International Nuclear Information System (INIS)

    Rezaei, Behzad; Keyvanfard, Mohsen

    2008-01-01

    In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at λ max = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL (ΔA = 0.2819C Ru + 1.1840) and 20.0-100.0 ng/mL (ΔA = 0.0984C Ru + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 ± 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples

  1. Mesoporous Fe-containing ZSM-5 zeolite single crystal catalysts for selective catalytic reduction of nitric oxide by ammonia

    DEFF Research Database (Denmark)

    Kustov, Arkadii; Egeblad, Kresten; Kustova, Marina

    2007-01-01

    Mesoporous and conventional Fe-containing ZSM-5 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnationmethod and tested in NO selective catalytic reduction (SCR) with NH3. It was found that mesoporous Fe-ZSM-5 catalysts exhibit higher SCR activities than comparable conventional cataly...

  2. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  3. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  4. 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 ...

  5. 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}.

  6. Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

    Directory of Open Access Journals (Sweden)

    Hamed Alshammari

    2017-10-01

    Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

  7. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields

  8. Improvement of Toluene Selectivity via the Application of an Ethanol Oxidizing Catalytic Cell Upstream of a YSZ-Based Sensor for Air Monitoring Applications

    Science.gov (United States)

    Sato, Tomoaki; Breedon, Michael; Miura, Norio

    2012-01-01

    The sensing characteristics of a yttria-stabilized zirconia (YSZ)-based sensor utilizing a NiO sensing-electrode (SE) towards toluene (C7H8) and interfering gases (C3H6, H2, CO, NO2 and C2H5OH) were evaluated with a view to selective C7H8 monitoring in indoor atmospheres. The fabricated YSZ-based sensor showed preferential responses toward 480 ppb C2H5OH, rather than the target 50 ppb C7H8 at an operational temperature of 450 °C under humid conditions (RH ≃ 32%). To overcome this limitation, the catalytic activity of Cr2O3, SnO2, Fe2O3 and NiO powders were evaluated for their selective ethanol oxidation ability. Among these oxides, SnO2 was found to selectively oxidize C2H5OH, thus improving C7H8 selectivity. An inline pre-catalytic cell loaded with SnO2 powder was installed upstream of the YSZ-based sensor utilizing NiO-SE, which enabled the following excellent abilities by selectively catalyzing common interfering gases; sensitive ppb level detection of C7H8 lower than the established Japanese Guideline value; low interferences from 50 ppb C3H6, 500 ppb H2, 100 ppb CO, 40 ppb NO2, as well as 480 ppb C2H5OH. These operational characteristics are all indicative that the developed sensor may be suitable for real-time C7H8 concentration monitoring in indoor environments. PMID:22666053

  9. Improvement of catalytic activity in selective oxidation of styrene with H{sub 2}O{sub 2} over spinel Mg–Cu ferrite hollow spheres in water

    Energy Technology Data Exchange (ETDEWEB)

    Tong, Jinhui, E-mail: jinhuitong@126.com [Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Lanzhou 730070 (China); Key Laboratory of Gansu Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Cai, Xiaodong; Wang, Haiyan; Zhang, Qianping [Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Lanzhou 730070 (China); Key Laboratory of Gansu Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2014-07-01

    Graphical abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. Solid spinel Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods for comparison. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be magnetically separated easily for reuse and no obvious loss of activity was observed when reused in six consecutive runs. - Highlights: • Uniform spinel ferrite hollow spheres were prepared by a simple method. • The catalyst has been proved much more efficient for styrene oxidation than the reported analogues. • The catalyst can be easily separated by external magnetic field and has exhibited excellent reusability. • The catalytic system is environmentally friendly. - Abstract: Uniform spinel Mg–Cu ferrite hollow spheres were prepared using carbon spheres as templates. For comparison, solid Mg–Cu ferrite nanocrystals were also prepared by sol–gel auto-combustion, hydrothermal and coprecipitation methods. All the samples were characterized by Fourier transform infrared spectrophotometry (FT-IR), X-ray diffractometry (XRD), transmission electron microscopy (TEM) and N{sub 2} physisorption. The samples were found to be efficient catalysts for oxidation of styrene using hydrogen peroxide as oxidant. Especially, in the case of Mg{sub 0.5}Cu{sub 0.5}Fe{sub 2}O{sub 4} hollow spheres, obvious improvement on catalytic activity was observed, and 21.2% of styrene conversion and 75.2% of selectivity for benzaldehyde were obtained at 80 °C for 6 h reaction in water. The catalyst can be

  10. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao; Croue, Jean-Philippe

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation

  11. 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...

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

    DEFF Research Database (Denmark)

    Møller, Jacob; Munk, Bjarne; Crillesen, Kim

    2011-01-01

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

  13. 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....

  14. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane; Reduction catalytique selective des oxydes d'azote (NO{sub x}) provenant d'effluents gazeux industriels par l'hydrogene ou le methane

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

    This work deals with the selective catalytic reduction of nitrogen oxides (NO{sub 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{sub 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{sub 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.)

  15. Molecular Components of Catalytic Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-07-02

    Selectivity, that is, to produce one molecule out of many other thermodynamically feasible product molecules, is the key concept to develop 'clean manufacturing' processes that do not produce byproducts (green chemistry). Small differences in potential energy barriers for elementary reaction steps control which reaction channel is more likely to yield the desired product molecule (selectivity), instead of the overall activation energy for the reaction that controls turnover rates (activity). Recent studies have demonstrated the atomic- or molecular-level tailoring of parameters such as the surface structures of active sites that give rise to nanoparticle size and shape dependence of turnover rates and reaction selectivities. Here, we highlight seven molecular components that influence reaction selectivities. These include: surface structure, adsorbate-induced restructuring, adsorbate mobility, reaction intermediates, surface composition, charge transport, and oxidation states for model metal single crystal and colloid nanoparticle catalysts. We show examples of their functioning and describe in-situ instruments that permit us to investigate their roles in surface reactions.

  16. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend.

    Science.gov (United States)

    Godoi, Ricardo H M; Polezer, Gabriela; Borillo, Guilherme C; Brown, Andrew; Valebona, Fabio B; Silva, Thiago O B; Ingberman, Aline B G; Nalin, Marcelo; Yamamoto, Carlos I; Potgieter-Vermaak, Sanja; Penteado Neto, Renato A; de Marchi, Mary Rosa R; Saldiva, Paulo H N; Pauliquevis, Theotonio; Godoi, Ana Flavia L

    2016-08-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP(ESR)) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP(ESR) results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100cm(-1) and 1600cm(-1) indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. A non-chemically selective top-down approach towards the preparation of hierarchical TS-1 zeolites with improved oxidative desulfurization catalytic performance.

    Science.gov (United States)

    Du, Shuting; Chen, Xiaoxin; Sun, Qiming; Wang, Ning; Jia, Mingjun; Valtchev, Valentin; Yu, Jihong

    2016-02-28

    Hierarchical TS-1 zeolites with secondary macropores have been successfully prepared by using two different fluoride-containing chemical etching post-treated routes. Hierarchical TS-1 zeolites exhibited a chemical composition similar to that of the parent material and showed remarkably enhanced catalytic activity in oxidative desulfurization reaction.

  18. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend

    International Nuclear Information System (INIS)

    Godoi, Ricardo H.M.; Polezer, Gabriela; Borillo, Guilherme C.; Brown, Andrew; Valebona, Fabio B.; Silva, Thiago O.B.; Ingberman, Aline B.G.; Nalin, Marcelo; Yamamoto, Carlos I.; Potgieter-Vermaak, Sanja; Penteado Neto, Renato A.; Marchi, Mary Rosa R. de; Saldiva, Paulo H.N.; Pauliquevis, Theotonio; Godoi, Ana Flavia L.

    2016-01-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP"E"S"R) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP"E"S"R results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100 cm"−"1 and 1600 cm"−"1 indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. - Highlights: • PM emission from biodiesel burning may be more harmful to human health than diesel. • Euro V (SCR) engine fuelled with B5 and B20 tested in a bench dynamometer • Electron Spin Resonance (ESR) to access the oxidative potential of PM emission

  19. Influence on the oxidative potential of a heavy-duty engine particle emission due to selective catalytic reduction system and biodiesel blend

    Energy Technology Data Exchange (ETDEWEB)

    Godoi, Ricardo H.M., E-mail: rhmgodoi@ufpr.br [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Polezer, Gabriela; Borillo, Guilherme C. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Brown, Andrew [Division of Chemistry and Environmental Science, School of Science and the Environment, Manchester Metropolitan University, Manchester (United Kingdom); Valebona, Fabio B.; Silva, Thiago O.B.; Ingberman, Aline B.G. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Nalin, Marcelo [LAVIE - Institute of Chemistry, São Paulo State University - UNESP, Araraquara (Brazil); Yamamoto, Carlos I. [Chemical Engineering Department, Federal University of Parana, Curitiba, PR (Brazil); Potgieter-Vermaak, Sanja [Division of Chemistry and Environmental Science, School of Science and the Environment, Manchester Metropolitan University, Manchester (United Kingdom); Penteado Neto, Renato A. [Vehicle Emissions Laboratory, Institute of Technology for Development (LACTEC), Curitiba, PR (Brazil); Marchi, Mary Rosa R. de [Analytical Chemistry Department, Institute of Chemistry, São Paulo State University - UNESP, Araraquara (Brazil); Saldiva, Paulo H.N. [Laboratory of Experimental Air Pollution, Department of Pathology, School of Medicine, University of São Paulo, São Paulo (Brazil); Pauliquevis, Theotonio [Department of Natural and Earth Sciences, Federal University of São Paulo, Diadema (Brazil); Godoi, Ana Flavia L. [Environmental Engineering Department, Federal University of Parana, Curitiba, PR (Brazil)

    2016-08-01

    Although the particulate matter (PM) emissions from biodiesel fuelled engines are acknowledged to be lower than those of fossil diesel, there is a concern on the impact of PM produced by biodiesel to human health. As the oxidative potential of PM has been suggested as trigger for adverse health effects, it was measured using the Electron Spin Resonance (OP{sup ESR}) technique. Additionally, Energy Dispersive X-ray Fluorescence Spectroscopy (EDXRF) was employed to determine elemental concentration, and Raman Spectroscopy was used to describe the amorphous carbon character of the soot collected on exhaust PM from biodiesel blends fuelled test-bed engine, with and without Selective Catalytic Reduction (SCR). OP{sup ESR} results showed higher oxidative potential per kWh of PM produced from a blend of 20% soybean biodiesel and 80% ULSD (B20) engine compared with a blend of 5% soybean biodiesel and 95% ULSD (B5), whereas the SCR was able to reduce oxidative potential for each fuel. EDXRF data indicates a correlation of 0.99 between concentration of copper and oxidative potential. Raman Spectroscopy centered on the expected carbon peaks between 1100 cm{sup −1} and 1600 cm{sup −1} indicate lower molecular disorder for the B20 particulate matter, an indicative of a more graphitic carbon structure. The analytical techniques used in this study highlight the link between biodiesel engine exhaust and increased oxidative potential relative to biodiesel addition on fossil diesel combustion. The EDXRF analysis confirmed the prominent role of metals on free radical production. As a whole, these results suggest that 20% of biodiesel blends run without SCR may pose an increased health risk due to an increase in OH radical generation. - Highlights: • PM emission from biodiesel burning may be more harmful to human health than diesel. • Euro V (SCR) engine fuelled with B5 and B20 tested in a bench dynamometer • Electron Spin Resonance (ESR) to access the oxidative potential of

  20. Environmentally friendly synthesis of CeO2 nanoparticles for the catalytic oxidation of benzyl alcohol to benzaldehyde and selective detection of nitrite.

    Science.gov (United States)

    Tamizhdurai, P; Sakthinathan, Subramanian; Chen, Shen-Ming; Shanthi, K; Sivasanker, S; Sangeetha, P

    2017-04-13

    Cerium oxide nanoparticles (CeO 2 NPs) are favorable in nanotechnology based on some remarkable properties. In this study, the crystalline CeO 2 NPs are successfully prepared by an efficient microwave combustion (MCM) and conventional route sol-gel (CRSGM) methods. The structural morphology of the as-prepared CeO 2 NPs was investigated by various spectroscopic and analytical techniques. Moreover, the XRD pattern confirmed the formation of CeO 2 NPs as a face centered cubic structure. The magnetometer studies indicated the low saturation magnetization (23.96 emu/g) of CeO 2 NPs for weak paramagnetic and high saturation magnetization (32.13 emu/g) of CeO 2 NPs for super paramagnetic. After that, the oxidation effect of benzyl alcohol was investigated which reveals good conversion and selectivity. Besides, the CeO 2 NPs modified glassy carbon electrode (GCE) used for the detection of nitrite with linear concentration range (0.02-1200 μM), low limit of detection (0.21 μM) and higher sensitivity (1.7238 μAμM -1 cm -2 ). However, the CeO 2 NPs modified electrode has the fast response, high sensitivity and good selectivity. In addition, the fabricated electrode is applied for the determination of nitrite in various water samples. Eventually, the CeO 2 NPs can be regarded as an effective way to enhance the catalytic activity towards the benzyl alcohol and nitrite.

  1. 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.

  2. A review of carbon-based and non-carbon-based catalyst supports for the selective catalytic reduction of nitric oxide.

    Science.gov (United States)

    Anthonysamy, Shahreen Binti Izwan; Afandi, Syahidah Binti; Khavarian, Mehrnoush; Mohamed, Abdul Rahman Bin

    2018-01-01

    Various types of carbon-based and non-carbon-based catalyst supports for nitric oxide (NO) removal through selective catalytic reduction (SCR) with ammonia are examined in this review. A number of carbon-based materials, such as carbon nanotubes (CNTs), activated carbon (AC), and graphene (GR) and non-carbon-based materials, such as Zeolite Socony Mobil-5 (ZSM-5), TiO 2 , and Al 2 O 3 supported materials, were identified as the most up-to-date and recently used catalysts for the removal of NO gas. The main focus of this review is the study of catalyst preparation methods, as this is highly correlated to the behaviour of NO removal. The general mechanisms involved in the system, the Langmuir-Hinshelwood or Eley-Riedeal mechanism, are also discussed. Characterisation analysis affecting the surface and chemical structure of the catalyst is also detailed in this work. Finally, a few major conclusions are drawn and future directions for work on the advancement of the SCR-NH 3 catalyst are suggested.

  3. Selective catalytic reduction of NO{sub x} with NH{sub 3} over iron-cerium-tungsten mixed oxide catalyst prepared by different methods

    Energy Technology Data Exchange (ETDEWEB)

    Xiong, Zhi-bo, E-mail: xzb328@163.com [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Collaborative Innovation Research Institute, University of Shanghai for Science & Technology, Shanghai 200093 (China); Shanghai Power Equipment Research Institute, Shanghai 200240 (China); Liu, Jing; Zhou, Fei; Liu, Dun-yu; Lu, Wei [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Jin, Jing [School of Energy and Power Engineering, University of Shanghai for Science & Technology, Shanghai 200093 (China); Collaborative Innovation Research Institute, University of Shanghai for Science & Technology, Shanghai 200093 (China); Ding, Shi-fa [Shanghai Power Equipment Research Institute, Shanghai 200240 (China)

    2017-06-01

    Highlights: • Iron-cerium-tungsten mixed oxide catalysts were prepared through three different methods. • The effect of preparation methods on the NH{sub 3}-SCR activity and the surface structure properties of catalyst were investigated. • Iron-cerium-tungsten mixed oxide prepared through microwave irradiation assistant critic acid sol-gel shows higher NH{sub 3}-SCR activity. - Abstract: A series of magnetic Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z} catalysts were synthesized by three different methods(Co-precipitation(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-CP), Hydrothermal treatment assistant critic acid sol-gel method(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-HT) and Microwave irradiation assistant critic acid sol-gel method(Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW)), and the catalytic activity was evaluated for selective catalytic reduction of NO with NH{sub 3}. The catalyst was characterized by XRD, N{sub 2} adsorption-desorption, XPS, H{sub 2}-TPR and NH{sub 3}-TPD. Among the tested catalysts, Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW shows the highest NO{sub x} conversion over per gram in unit time with NO{sub x} conversion of 60.8% at 350 °C under a high gas hourly space velocity of 1,200,000 ml/(g h). Different from Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-CP catalyst, there exists a large of iron oxide crystallite(γ-Fe{sub 2}O{sub 3} and α-Fe{sub 2}O{sub 3}) scattered in Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z} catalysts prepared through hydrothermal treatment or microwave irradiation assistant critic acid sol-gel method, and higher iron atomic concentration on their surface. And Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW shows higher surface absorbed oxygen concentration and better dispersion compared with Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-HT catalyst. These features were favorable for the high catalytic performance of NO reduction with NH{sub 3} over Fe{sub 0.85}Ce{sub 0.10}W{sub 0.05}O{sub z}-MW catalyst.

  4. INDUSTRIAL BOILER RETROFIT FOR NOX CONTROL: COMBINED SELECTIVE NONCATALYTIC REDUCTION AND SELECTIVE CATALYTIC REDUCTION

    Science.gov (United States)

    The paper describes retrofitting and testing a 590 kW (2 MBtu/hr), oil-fired, three-pass, fire-tube package boiler with a combined selective noncatalytic reduction (SNCR) and selective catalytic reduction (SCR) system. The system demonstrated 85% nitrogen oxides (NOx) reduction w...

  5. The Enhancement of the Selectivity of Complex Reactions by a Catalytic Membrane Reactor -Ethylene Oxidation Over a Ag Catalyst Supported in a Ceramic Membrane-

    OpenAIRE

    馮, 臨; 小林, 正義; Lin, FENG; Masayoshi, KOBAYASHI

    1991-01-01

    This research demonstrated that, using a membrane reactor consisting of a tubular, microporous, glass-ceramic membrane, it is possible to achieve selective oxidation of ethylene to ethylene oxide with an Ag catalyst. In experiments which a reaction temperature range of 115 to 300℃ and a contact time of 1.5 to 5 seconds, resulting data illustrated the following characteristics of this membrane reactor : 1) compared with a classic tubular reactor, the selectivity of ethylene oxide is increased ...

  6. 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.

  7. Demonstration of Selective Catalytic Reduction Technology to Control Nitrogen Oxide Emissions From High-Sulfur, Coal-Fired Boilers: A DOE Assessment

    International Nuclear Information System (INIS)

    Federal Energy Technology Center

    1999-01-01

    The goal of the U.S. Department of Energy (DOE) Clean Coal Technology (CCT) program is to furnish the energy marketplace with a number of advanced, more efficient, and environmentally responsible coal utilization technologies through demonstration projects. These projects seek to establish the commercial feasibility of the most promising advanced coal technologies that have developed beyond the proof-of-concept stage. This document serves as a DOE post-project assessment of a project selected in CCT Round 2. The project is described in the report ''Demonstration of Selective Catalytic Reduction (SCR) Technology for the Control of Nitrogen Oxide (NO(sub x)) Emissions from High-Sulfur, Coal-Fired Boilers'' (Southern Company Services 1990). In June 1990, Southern Company Services (Southern) entered into a cooperative agreement to conduct the study. Southern was a cofunder and served as the host at Gulf Power Company's Plant Crist. Other participants and cofunders were EPRI (formerly the Electric Power Research Institute) and Ontario Hydro. DOE provided 40 percent of the total project cost of$23 million. The long-term operation phase of the demonstration was started in July 1993 and was completed in July 1995. This independent evaluation is based primarily on information from Southern's Final Report (Southern Company Services 1996). The SCR process consists of injecting ammonia (NH(sub 3)) into boiler flue gas and passing the 3 flue gas through a catalyst bed where the NO(sub x) and NH(sub 3) react to form nitrogen and water vapor. The objectives of the demonstration project were to investigate: Performance of a wide variety of SCR catalyst compositions, geometries, and manufacturing methods at typical U.S. high-sulfur coal-fired utility operating conditions; Catalyst resistance to poisoning by trace metal species present in U.S. coals but not present, or present at much lower concentrations, in fuels from other countries; and Effects on the balance-of-plant equipment

  8. 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.

  9. 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

  10. 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.

  11. COST OF SELECTIVE CATALYTIC REDUCTION (SCR) APPLICATION FOR NOX CONTROL ON COAL-FIRED BOILERS

    Science.gov (United States)

    The report provides a methodology for estimating budgetary costs associated with retrofit applications of selective catalytic reduction (SCR) technology on coal-fired boilers. SCR is a postcombustion nitrogen oxides (NOx) control technology capable of providing NOx reductions >90...

  12. Selective oxidation of i-butene and i-butene to methacrolein and methacrylic acid over Keggin-type polyoxometalate and MoVTeNbOx catalysts. A comparative catalytic and in situ-spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Bentrup, U.; Brueckner, A.; Kant, M.; Kolf, S.; Dingerdissen, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V. (Germany); Jansen, S.; Maschmeyer, D.; Sieger, H.; Zanthoff, H.W. [Degussa AG, Marl (Germany)

    2005-07-01

    An alternative to overcome the drawbacks connected with POM catalysts may be the development of suitable mixed metal oxide catalysts. MoVTeNbO{sub x} materials could be promising candidates since they revaled remarkable performance in the selective oxidation of propane to acrylic acid. However, up to now their behaviour in the selective oxidation of i-butane has rarely been studied. The investigations presented in this paper are focused on the interaction of feed components (i-butane / i-butene, O{sub 2}, H{sub 2}O) with Keggin-type polyoxometalate and MoVTeNbO{sub x} catalysts. FTIR spectroscopy was used to identify adsorbed intermediates and products while the novel simultaneous operando-EPR/UV-vis/Raman/GC technique revealed to be an excellent tool to follow the behaviour of V and Mo sites. In relation to the results of catalytic tests, structure-reactivity relationships are derived. (orig.)

  13. 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...

  14. 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.

  15. 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.

  16. 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

  17. The selective catalytic reduction of NO with NH3 over a novel Ce-Sn-Ti mixed oxides catalyst: Promotional effect of SnO2

    Science.gov (United States)

    Yu, Ming'e.; Li, Caiting; Zeng, Guangming; Zhou, Yang; Zhang, Xunan; Xie, Yin'e.

    2015-07-01

    A series of novel catalysts (CexSny) for the selective catalytic reduction of NO by NH3 were prepared by the inverse co-precipitation method. The aim of this novel design was to improve the NO removal efficiency of CeTi by the introduction of SnO2. It was found that the Ce-Sn-Ti catalyst was much more active than Ce-Ti and the best Ce:Sn molar ratio was 2:1. Ce2Sn1 possessed a satisfied NO removal efficiency at low temperature (160-280 °C), while over 90% NO removal efficiency maintained in the temperature range of 280-400 °C at the gas hourly space velocity (GHSV) of 50,000 h-1. Besides, Ce2Sn1 kept a stable NO removal efficiency within a wide range of GHSV and a long period of reacting time. Meanwhile, Ce2Sn1 exhibited remarkable resistance to both respectively and simultaneously H2O and SO2 poisoning due to the introduction of SnO2. The promotional effect of SnO2 was studied by N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and H2 temperature programmed reduction (H2-TPR) for detail information. The characterization results revealed that the excellent catalytic performance of Ce2Sn1 was associated with the higher specific surface area, larger pore volume and poorer crystallization. Besides, the introduction of SnO2 could result in not only greater conversion of Ce4+ to Ce3+ but also the increase amount of chemisorbed oxygen, which are beneficial to improve the SCR activity. More importantly, a novel peak appearing at lower temperatures through the new redox equilibrium of 2Ce4+ + Sn2+ ↔ 2Ce3+ + Sn4+ and higher total H2 consumption can be obtained by the addition of SnO2. Finally, the possible reaction mechanism of the selective catalytic reduction over Ce2Sn1 was also proposed.

  18. Development of selective catalytic oxidation (SCO) for NH{sub 3} and HCN removal from gasification gas; Selektiivisen katalyyttisen hapetusprosessin (SCO) kehittaeminen kaasutuskaasun NH{sub 3}:n ja HCN:n poistoon

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-10-01

    In gasification, reactive nitrogen compounds (mainly NH{sub 3} and HCN) are formed from fuel nitrogen. If the gas containing NH{sub 3} is burned, a high NO{sub x} emission may be formed. The content of nitrogen compounds of the hot gasification gas could be reduced in Selective Catalytic Oxidation (SCO) process. In this process small amounts of reactive oxidisers are injected into the gas in order to convert NH{sub 3} to N{sub 2}. The utilization of SCO process together with low NO{sub x} burners in advanced gasification power stations might offer an alternative for flue gas treatment technologies like SCR (Selective Catalytic Reduction). In the earlier research, conditions were found, where oxidizers reacted selectively with ammonia in the gasification gas. Highest ammonia reduction took place in the aluminium oxide bed in the presence of NO and O{sub 2}. The aim of this study is to examine the reaction mechanism in order to be able to further evaluate the development possibilities of this kind process. The effect of composition and the amount of added oxidizer, the content of combustible gas components, space velocity, pressure and temperature will be studied. The experiments are carried out with the laboratory scale high pressure flow reactor of VTT Energy. Kinetic modelling of the experimental results is carried out in co-operation with the combustion chemistry group of Aabo Akademi. The aim of the modelling work is to bring insight to the gas-phase reactions that are important for the SCO-process. (orig.)

  19. 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.

  20. 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

  1. 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.

  2. Multi-stage selective catalytic reduction of NOx in lean burn engine exhaust

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-12-31

    Many studies suggest that the conversion of NO to NO{sub 2} is an important intermediate step in the selective catalytic reduction (SCR) of NO{sub x} to N{sub 2}. Some effort has been devoted to separating the oxidative and reductive functions of the catalyst in a multi-stage system. This method works fine for systems that require hydrocarbon addition. The hydrocarbon has to be injected between the NO oxidation catalyst and the NO{sub 2} reduction catalyst; otherwise, the first-stage oxidation catalyst will also oxidize the hydrocarbon and decrease its effectiveness as a reductant. The multi-stage catalytic scheme is appropriate for diesel engine exhausts since they contain insufficient hydrocarbons for SCR, and the hydrocarbons can be added at the desired location. For lean-burn gasoline engine exhausts, the hydrocarbons already present in the exhausts will make it necessary to find an oxidation catalyst that can oxidize NO to NO{sub 2} but not oxidize the hydrocarbon. A plasma can also be used to oxidize NO to NO{sub 2}. Plasma oxidation has several advantages over catalytic oxidation. Plasma-assisted catalysis can work well for both diesel engine and lean-burn gasoline engine exhausts. This is because the plasma can oxidize NO in the presence of hydrocarbons without degrading the effectiveness of the hydrocarbon as a reductant for SCR. In the plasma, the hydrocarbon enhances the oxidation of NO, minimizes the electrical energy requirement, and prevents the oxidation of SO{sub 2}. This paper discusses the use of multi-stage systems for selective catalytic reduction of NO{sub x}. The multi-stage catalytic scheme is compared to the plasma-assisted catalytic scheme.

  3. 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...

  4. Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

    2017-01-01

    The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

  5. Selective catalytic reduction of NO{sub x} by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Radtke, F

    1997-12-31

    The removal of nitrogen oxides from the exhaust of lean-burn gasoline fuelled and diesel-fuelled engines, operating under net oxidizing conditions, has recently attracted considerable attention. In this work, three different catalytic systems (Al{sub 2}O{sub 3}, Cu/Al{sub 2}O{sub 3} and Cu/ZSM-5) are investigated for their suitability as catalysts for the selective reduction of nitrogen oxides by hydrocarbons in excess oxygen. Special emphasis is given to the formation of potentially harmful byproducts such as hydrogen cyanide (HCN), cyanic acid (HNCO), ammonia (NH{sub 3}) and nitrous oxide (N{sub 2}O). The effect of reaction temperature, nitrogen oxide (NO, NO{sub 2}), hydrocarbon (ethene, propene) and water on activity and the formation of byproducts is investigated. In situ FTIR spectroscopy and temperature-programmed surface reactions (TPSR) of absorbed species in different atmospheres were used to investigate the nature and reactivity of adsorbates formed under reaction conditions. The catalytic activity was strongly influenced by the presence of water in the feed. The effects of the other parameters were suppressed and the performance generally decreased, except when propene was used for the reduction of NO{sub x} over Cu/ZSM-5. Over Cu/ZSM-5 clearly higher conversion was obtained, when ethene was used as reducing agent, while there was no significant difference when starting from NO or NO{sub 2}. In contrast, with {gamma}-Al{sub 2}O{sub 3} NO{sub 2} was reduced more efficiently than NO with both reductants. The impregnation of {gamma}-Al{sub 2}O{sub 3} with copper led to an extensive loss of this performance. For dry feeds and with increasing CuO loading, the catalysts reached maximum activity at lower temperature and the maximum yield of nitrogen slightly decreased. (author) figs., tabs., refs.

  6. 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

  7. 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

  8. 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.

  9. 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

  10. Substrate-Directed Catalytic Selective Chemical Reactions.

    Science.gov (United States)

    Sawano, Takahiro; Yamamoto, Hisashi

    2018-05-04

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-03-01

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

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

    Science.gov (United States)

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

    2016-04-04

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

  13. 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...

  14. 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

  15. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane; Reduction catalytique selective des oxydes d'azote (NO{sub x}) provenant d'effluents gazeux industriels par l'hydrogene ou le methane

    Energy Technology Data Exchange (ETDEWEB)

    Engelmann Pirez, M

    2004-12-15

    This work deals with the selective catalytic reduction of nitrogen oxides (NO{sub 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{sub 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{sub 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.)

  16. 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...

  17. 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.)

  18. Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

    DEFF Research Database (Denmark)

    Zahrtmann, Nanette; Claver, Carmen; Godard, Cyril

    2018-01-01

    A catalytic system for the selective oxidative carbonylation of aniline to diphenylurea based on Pd complexes in combination with imidazolium ionic liquids is presented. Both oxidants, Pd complexes and ionic liquids affect the activity of the reaction while the choice of oxidant determines...

  19. 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

  20. 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#

  1. 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 ...

  2. 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...

  3. Selective oxidation of propane over cation exchanged zeolites

    NARCIS (Netherlands)

    Xu, J.

    2005-01-01

    This thesis focuses on investigation of the fundamental knowledge on a new method for selective oxidation of propane with O2 at low temperature (< 100°C). The relation between propane catalytic selective oxidation and physicochemical properties of cation exchanged Y zeolite has been studied. An

  4. 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.

  5. 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...

  6. 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.

  7. Multi-Stage Selective Catalytic Reduction of NOx in Lean-Burn Engine Exhaust

    National Research Council Canada - National Science Library

    Penetrante, B

    1997-01-01

    .... A plasma can also be used to oxidize NO to NO2. This paper compares the multi-stage catalytic scheme with the plasma-assisted catalytic scheme for reduction of NOx in lean-burn engine exhausts. The advantages of plasma oxidation over catalytic oxidation are presented.

  8. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K; Kumar, N; Lindfors, L E [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1997-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  9. Selective catalytic reduction of nitric oxide by ethylene over metal-modified ZSM-5- and {gamma}-Al{sub 2}O{sub 3}-catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Eraenen, K.; Kumar, N.; Lindfors, L.E. [Aabo Akademi, Turku (Finland). Lab. of Industrial Chemistry

    1996-12-31

    Metal-modified ZSM-5 and {gamma}-Al{sub 2}O{sub 3} catalysts were tested in reduction of nitric oxide by ethylene. Different metals were introduced into the ZSM-5 catalyst by ion-exchange and by introduction of metals during the zeolite synthesis. To prepare bimetallic catalysts a combination of these methods was used. The {gamma}-Al{sub 2}O{sub 3} was impregnated with different metals by the incipient wetness technique and by adsorption. Activity measurements showed that the ZSM-5 based catalysts were more active than the {gamma}-Al{sub 2}O{sub 3} based catalysts. The highest conversion was obtained over a ZSM-5 catalyst prepared by introduction of Pd during synthesis of the zeolite and subsequently ion-exchanged with copper. (author)

  10. 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

  11. 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....

  12. Selective carbon monoxide oxidation over Ag-based composite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

    2002-02-01

    We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

  13. 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.

  14. 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.

  15. 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...

  16. 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

  17. 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.

  18. 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)

  19. 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.

  20. 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.

  1. Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, first and second quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from U.S., Japanese and European catalyst suppliers on a high-sulfur U.S. coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involve injecting ammonia into the flue gas generated from coal combustion in a boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and Europe on gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; and (3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The project is being conducted in the following three phases: permitting, environmental monitoring plan and preliminary engineering; detailed design engineering and construction; and operation, testing, disposition and final report. The project was in the operation and testing phase during this reporting period. Accomplishments for this period are described.

  2. Innovative Clean Coal Technology (ICCT): Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Technical progress report, third and fourth quarters 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-11-01

    The objective of this project is to demonstrate and evaluate commercially available selective catalytic reduction (SCR) catalysts from U.S., Japanese, and European catalyst suppliers on a high-sulfur U.S. Coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO{sub x}) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO{sub x} to form nitrogen and water vapor. Although SCR is widely practiced in Japan and European gas-, oil-, and low-sulfur coal-fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: (1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels; (2) performance of the technology and effects on the balance-of-plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}; performance of a wide variety of SCR catalyst compositions, geometries, and methods of manufacture under typical high-sulfur coal-fired utility operating conditions. These uncertainties are being explored by operating a series of small- scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. The demonstration is being performed at Gulf Power Company`s Plant Crist Unit No. 5 (75 MW capacity) near Pensacola, Florida. The project is funded by the U.S. Department of Energy (DOE), Southern Company Services, Inc. (SCS on behalf of the entire Southern electric system), the Electric Power Research Institute (EPRI), and Ontario Hydro. SCS is the participant responsible for managing al aspects of this project. 1 ref., 69 figs., 45 tabs.

  3. 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.

  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. 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.

  6. 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

  7. 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.

  8. Selective Oxidation of Lignin Model Compounds.

    Science.gov (United States)

    Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

    2018-05-02

    Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. A new experimental setup for high-pressure catalytic activity measurements on surface deposited mass-selected Pt clusters

    International Nuclear Information System (INIS)

    Watanabe, Yoshihide; Isomura, Noritake

    2009-01-01

    A new experimental setup to study catalytic and electronic properties of size-selected clusters on metal oxide substrates from the viewpoint of cluster-support interaction and to formulate a method for the development of heterogeneous catalysts such as automotive exhaust catalysts has been developed. The apparatus consists of a size-selected cluster source, a photoemission spectrometer, a scanning tunneling microscope (STM), and a high-pressure reaction cell. The high-pressure reaction cell measurements provided information on catalytic properties in conditions close to practical use. The authors investigated size-selected platinum clusters deposited on a TiO 2 (110) surface using a reaction cell and STM. Catalytic activity measurements showed that the catalytic activities have a cluster-size dependency.

  18. 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)

  19. 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.

  20. 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.

  1. 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.

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

    KAUST Repository

    Zhang, Tao

    2011-11-01

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

  3. 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.

  4. 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...

  5. 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.

  6. 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.

  7. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

    Science.gov (United States)

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2014-11-24

    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Selective propene oxidation on mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    James, David William

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

  13. Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Y.; Grass, M.E.; Kuhn, J.N.; Tao, F.; Habas, S.E.; Huang, W.; Yang, P.; Somorjai, G.A.

    2009-02-21

    Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, horns and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl

  14. 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.

  15. 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.

  16. 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.

  17. Uniformity index measurement technology using thermocouples to improve performance in urea-selective catalytic reduction systems

    Science.gov (United States)

    Park, Sangki; Oh, Jungmo

    2018-05-01

    The current commonly used nitrogen oxides (NOx) emission reduction techniques employ hydrocarbons (HCs), urea solutions, and exhaust gas emissions as the reductants. Two of the primary denitrification NOx (DeNOx) catalyst systems are the HC-lean NOx trap (HC-LNT) catalyst and urea-selective catalytic reduction (urea-SCR) catalyst. The secondary injection method depends on the type of injector, injection pressure, atomization, and spraying technique. In addition, the catalyst reaction efficiency is directly affected by the distribution of injectors; hence, the uniformity index (UI) of the reductant is very important and is the basis for system optimization. The UI of the reductant is an indicator of the NOx conversion efficiency (NCE), and good UI values can reduce the need for a catalyst. Therefore, improving the UI can reduce the cost of producing a catalytic converter, which are expensive due to the high prices of the precious metals contained therein. Accordingly, measurement of the UI is an important process in the development of catalytic systems. Two of the commonly used methods for measuring the reductant UI are (i) measuring the exhaust emissions at many points located upstream/downstream of the catalytic converter and (ii) acquisition of a reductant distribution image on a section of the exhaust pipe upstream of the catalytic converter. The purpose of this study is to develop a system and measurement algorithms to measure the exothermic response distribution in the exhaust gas as the reductant passes through the catalytic converter of the SCR catalyst system using a set of thermocouples downstream of the SCR catalyst. The system is used to measure the reductant UI, which is applied in real-time to the actual SCR system, and the results are compared for various types of mixtures for various engine operating conditions and mixer types in terms of NCE.

  18. 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.

  19. 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 ...

  20. 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?

  1. 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?

  2. 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.

  3. 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...

  4. 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.

  5. 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.

  6. 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.

  7. 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...

  8. Mean field approximation for the kinetics of the selective catalytic reduction of NO by ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Santos, M.; Bodanese, J.P. [Centro de Ensino Sao Jose, Universidade do Vale do Itajai (Brazil); S. Grandi, B.C. da [Departamento de Fisica, Universidade Federal de Santa Catarina, Florianopolis (Brazil)

    2007-04-15

    In this work we study a catalytic reaction model among three monomers in order to understand the chemical kinetics of the selective catalytic reduction of nitrogen oxide by ammonia (4NO+4NH{sub 3}+O{sub 2}{yields}4N{sub 2}+6H{sub 2}O). Our model takes into account the formation of the intermediate species in the global scheme of the reaction. In order to determine the dynamical behaviour of the model we used single site approximation method. In this approach we have observed that, depending on the values of the control parameters, the model presents an active or an inactive phase. In fact, the dynamical phase diagram of the model exhibits a first order line separating these two phases. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  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. Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

    1995-06-01

    This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

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

    Science.gov (United States)

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

    2013-05-28

    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.

  12. 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.)

  13. 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

  14. 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)

  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. 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....

  17. 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.

  18. 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.

  19. 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)

  20. Problems of selectivity in liquid-phase oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Emanuel, N M

    1978-07-01

    Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

  1. A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

    DEFF Research Database (Denmark)

    1999-01-01

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

  2. 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.

  3. Experimental investigation on emission reduction in neem oil biodiesel using selective catalytic reduction and catalytic converter techniques.

    Science.gov (United States)

    Viswanathan, Karthickeyan

    2018-05-01

    In the present study, non-edible seed oil namely raw neem oil was converted into biodiesel using transesterification process. In the experimentation, two biodiesel blends were prepared namely B25 (25% neem oil methyl ester with 75% of diesel) and B50 (50% neem oil methyl ester with 50% diesel). Urea-based selective catalytic reduction (SCR) technique with catalytic converter (CC) was fixed in the exhaust tail pipe of the engine for the reduction of engine exhaust emissions. Initially, the engine was operated with diesel as a working fluid and followed by refilling of biodiesel blends B25 and B50 to obtain the baseline readings without SCR and CC. Then, the same procedure was repeated with SCR and CC technique for emission reduction measurement in diesel, B25 and B50 sample. The experimental results revealed that the B25 blend showed higher break thermal efficiency (BTE) and exhaust gas temperature (EGT) with lower break-specific fuel consumption (BSFC) than B50 blend at all loads. On comparing with biodiesel blends, diesel experiences increased BTE of 31.9% with reduced BSFC of 0.29 kg/kWh at full load. A notable emission reduction was noticed for all test fuels in SCR and CC setup. At full load, B25 showed lower carbon monoxide (CO) of 0.09% volume, hydrocarbon (HC) of 24 ppm, and smoke of 14 HSU and oxides of nitrogen (NOx) of 735 ppm than diesel and B50 in SCR and CC setup. On the whole, the engine with SCR and CC setup showed better performance and emission characteristics than standard engine operation.

  4. Research advances in the catalysts for the selective oxidation of ethane to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhe; ZHAO Zhen; XU Chunming

    2005-01-01

    Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

  5. Innovative clean coal technology (ICCT): demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NOx) emission from high-sulfur, coal-fired boilers - economic evaluation of commercial-scale SCR applications for utility boilers

    International Nuclear Information System (INIS)

    Healy, E.C.; Maxwell, J.D.; Hinton, W.S.

    1996-09-01

    This report presents the results of an economic evaluation produced as part of the Innovative Clean Coal Technology project, which demonstrated selective catalytic reduction (SCR) technology for reduction of NO x emissions from utility boilers burning U.S. high-sulfur coal. The document includes a commercial-scale capital and O ampersand M cost evaluation of SCR technology applied to a new facility, coal-fired boiler utilizing high-sulfur U.S. coal. The base case presented herein determines the total capital requirement, fixed and variable operating costs, and levelized costs for a new 250-MW pulverized coal utility boiler operating with a 60-percent NO x removal. Sensitivity evaluations are included to demonstrate the variation in cost due to changes in process variables and assumptions. This report also presents the results of a study completed by SCS to determine the cost and technical feasibility of retrofitting SCR technology to selected coal-fired generating units within the Southern electric system

  6. 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)

  7. 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%.

  8. 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...

  9. 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

  10. 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

  11. 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.

  12. Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-01-01

    Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

  13. Catalytic selective reduction of NO with ethylene over a series of copper catalysts on amorphous silicas

    International Nuclear Information System (INIS)

    Carniti, P.; Gervasini, A.; Modica, V.H.; Ravasio, N.

    2000-01-01

    Catalytic selective reduction of NO to N 2 was studied comparing a series of Cu-based catalysts (ca. 8wt.%) supported over amorphous pure and modified silicas: SiO 2 , SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , SiO 2 -ZrO 2 . The catalysts were prepared by the chemisorption-hydrolysis method which ensured the formation of a unique copper phase well dispersed over all supports, as confirmed by scanning electron micrographs (SEMs). Temperature-programmed reduction (TPR) analyses confirmed the presence of dispersed copper species which underwent complete reduction at a temperature of about 220C, independently of the support. It was found that the support affects the extent of NO reduction as well as the selectivity to N 2 formation. Maximum N 2 yield was found in the range 275-300C. The catalyst prepared over SiO 2 -Al 2 O 3 was the most active and selective with respect to the other silicas. Competitiveness factors (c.f.'s) as high as 13-20% in the temperature range 200-250C could be calculated. For all catalysts, the temperature of the N 2 peak maximum did not correspond to that of the maximum C 2 H 4 oxidation to CO 2 , suggesting the presence of two different sites for the oxidation and the reduction activity. On the catalyst prepared on SiO 2 -Al 2 O 3 , a kinetic interpretation of catalytic data collected at different contact times and temperatures permitted evaluating the ratio between kinetic coefficients as well as the difference between activation energies of NO reduction by C 2 H 4 and C 2 H 4 oxidation by O 2

  14. 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...

  15. 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

  16. 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.

  17. 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

  18. Alkali resistivity of Cu based selective catalytic reduction catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Jensen, Anker Degn; Riisager, Anders

    2012-01-01

    The deactivation of V2O5–WO3–TiO2, Cu–HZSM5 and Cu–HMOR plate type monolithic catalysts was investigated when exposed to KCl aerosols in a bench-scale reactor. Fresh and exposed catalysts were characterized by selective catalytic reduction (SCR) activity measurements, scanning electron microscope......–energy dispersive X-ray spectroscopy (SEM–EDX) and NH3-temperature programmed desorption (NH3-TPD). 95% deactivation was observed for the V2O5–WO3–TiO2 catalyst, while the Cu–HZSM5 and Cu–HMOR catalysts deactivated only 58% and 48%, respectively, after 1200 h KCl exposure. SEM analysis of the KCl aerosol exposed...... catalysts revealed that the potassium salt not only deposited on the catalyst surface, but also penetrated into the catalyst wall. Thus, the K/M ratio (M = V or Cu) was high on V2O5–WO3–TiO2 catalyst and comparatively less on Cu–HZSM5 and Cu–HMOR catalysts. NH3-TPD revealed that the KCl exposed Cu–HZSM5...

  19. Effect of high-temperature treatment on Fe/ZSM-5 prepared by chemical vapor deposition of FeCl3. II. Nitrous oxide decomposition, selective oxidation of benzene to phenol, and selective reduction of nitric oxide by isobutane

    NARCIS (Netherlands)

    Zhu, Q.; Teeffelen, van R.M.; Santen, van R.A.; Hensen, E.J.M.

    2004-01-01

    The catalytic performance (nitrous oxide decomposition, hydroxylation of benzene to phenol with nitrous oxide, and selective reduction of nitric oxide by i-butane) was evaluated for a set of HZSM-5 and sublimed Fe/ZSM-5 catalysts, which have been extensively characterized in an earlier contribution

  20. 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

  1. 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)

  2. SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS

    Science.gov (United States)

    We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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)

  9. 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.

  10. Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher

    2011-01-01

    Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.

  11. 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

  12. 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)

  13. 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.

  14. Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

    Science.gov (United States)

    Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

    2016-12-19

    We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A Dynamic Supramolecular System Exhibiting Substrate Selectivity in the Catalytic Epoxidation of Olefins

    DEFF Research Database (Denmark)

    Jonsson, Stefan; Odille, Fabrice G. J.; Norrby, Per-Ola

    2005-01-01

    A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction.......A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction....

  16. 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....

  17. 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,...

  18. 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)

  19. 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

  20. 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)

  1. 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 ...

  2. Efficient selective catalytic reduction of NO by novel carbon-doped metal catalysts made from electroplating sludge.

    Science.gov (United States)

    Zhang, Jia; Zhang, Jingyi; Xu, Yunfeng; Su, Huimin; Li, Xiaoman; Zhou, Ji Zhi; Qian, Guangren; Li, Li; Xu, Zhi Ping

    2014-10-07

    Electroplating sludges, once regarded as industrial wastes, are precious resources of various transition metals. This research has thus investigated the recycling of an electroplating sludge as a novel carbon-doped metal (Fe, Ni, Mg, Cu, and Zn) catalyst, which was different from a traditional carbon-supported metal catalyst, for effective NO selective catalytic reduction (SCR). This catalyst removed >99.7% NO at a temperature as low as 300 °C. It also removed NO steadily (>99%) with a maximum specific accumulative reduced amount (MSARA) of 3.4 mmol/g. Gas species analyses showed that NO removal was accompanied by evolving N2 and CO2. Moreover, in a wide temperature window, the sludge catalyst showed a higher CO2 selectivity (>99%) than an activated carbon-supported metal catalyst. Structure characterizations revealed that carbon-doped metal was transformed to metal oxide in the sludge catalyst after the catalytic test, with most carbon (2.33 wt %) being consumed. These observations suggest that NO removal over the sludge catalyst is a typical SCR where metals/metal oxides act as the catalytic center and carbon as the reducing reagent. Therefore, our report probably provides an opportunity for high value-added utilizations of heavy-metal wastes in mitigating atmospheric pollutions.

  3. 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)

  4. Selective catalytic reduction system and process for control of NO.sub.x emissions in a sulfur-containing gas stream

    Science.gov (United States)

    Sobolevskiy, Anatoly

    2015-08-11

    An exhaust gas treatment process, apparatus, and system for reducing the concentration of NOx, CO and hydrocarbons in a gas stream, such as an exhaust stream (29), via selective catalytic reduction with ammonia is provided. The process, apparatus and system include a catalytic bed (32) having a reducing only catalyst portion (34) and a downstream reducing-plus-oxidizing portion (36). Each portion (34, 36) includes an amount of tungsten. The reducing-plus-oxidizing catalyst portion (36) advantageously includes a greater amount of tungsten than the reducing catalyst portion (36) to markedly limit ammonia salt formation.

  5. 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)

  6. 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.

  7. 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.

  8. 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.)

  9. Effect of antimony oxide on magnesium vanadates for the selective oxidation of hydrogen sulfide to sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Li, K.T.; Chi, Z.H. [Department of Chemical Engineering, Tunghai University, ROC Taichung (Taiwan)

    2001-05-17

    The effect of antimony oxide addition to MgV{sub 2}O{sub 6} and Mg{sub 3}V{sub 2}O{sub 8} was studied in the selective oxidation of hydrogen sulfide to sulfur. Significant improvements in sulfur selectivity and yield were observed for the uncalcined mechanical mixtures of magnesium vanadates with {alpha}-Sb{sub 2}O{sub 4}. Calcination of the mechanical mixtures resulted in the much stronger synergy in catalytic activity and sulfur selectivity. For the uncalcined samples, XRD, TPR and XPS studies indicated that antimony reduction behaviors in the mechanical mixtures differed very much from those in {alpha}-Sb{sub 2}O{sub 4} alone, suggested that their selectivity improvements might be due to the interactions (probably oxygen transfer) between {alpha}-Sb{sub 2}O{sub 4} and magnesium vanadates. For the calcined samples, XRD results indicated that their better catalytic performances in H{sub 2}S oxidation were primarily attributed to the formation of VSbO{sub 4} compound from antimony oxide and magnesium vanadates.

  10. 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)

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

    OpenAIRE

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

    2013-01-01

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

  12. 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...

  13. Selective oxidations on vanadiumoxide containing amorphous mixed oxides (AMM-V) with tert.-butylhydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Y.; Hunnius, M.; Storck, S.; Maier, W.F. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)

  14. Selective catalytic reduction of nitrogen oxide. Pt. 2. Side flow system for the provision of gaseous ammonia; Selektive katalytische Reduktion von Strickoxiden. T. 2. Nebenstromverfahren zur Bereitstellung gasfoermigen Ammoniaks

    Energy Technology Data Exchange (ETDEWEB)

    Heubuch, Alexander; Wachtmeister, Georg [Technische Univ. Muenchen (Germany). Lehrstuhl fuer Verbrennungskraftmaschinen; Toshev, Plamen [MAN Diesel and Turbo SE, Augsburg (Germany); Sattelmayer, Thomas [Technische Univ. Muenchen (Germany). Lehrstuhl fuer Thermodynamik

    2012-12-01

    The limitation of NO{sub x} emissions from diesel engines has been significantly tightened, among other things by the introduction of Euro 5 and Euro 6. In numerous applications on passenger car diesel engines, SCR catalytic converters were introduced to reduce NO{sub x} emissions in order to comply with the strict standards. Insufficient properties make the use of the required aqueous urea solution more difficult. The first part of this article published in MTZ 11 reported on the findings achieved at the Paul Scherrer Institute on the use of guanidinium formiate (GuFo) and its properties as an alternative to established urea SCR technology. In the second part, the TU Munich presents the application on a diesel engine and the ammonia generator (NH{sub 3} generator) with a bypass system developed for this purpose.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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

  20. 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...

  1. 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

  2. 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…

  3. 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

  4. 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 =

  5. 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.

  6. 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.)

  7. Selective Oxidation of Biomass-Derived Chemicals

    DEFF Research Database (Denmark)

    Modvig, Amalie Elise

    . These processes should be able to compete with the established processes based on fossil resources. Glycolaldehyde is an often-observed by-product formed from degradation of larger sugars. Due to competing ecological and economical aspects of the well-established processes for extraction and conversion....... The objective of this dissertation was to develop new, alternative and sustainable methods for oxidative catalytic upgrading of biomass-derived compounds, with focus on oxidation of glycolaldehyde and simple alcohols as model substrates for larger sugars. Supported gold nanoparticle were studied...

  8. 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.

  9. 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.

  10. 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.)

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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...

  1. 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.

  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. 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

  4. 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.

  5. 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.

  6. INVESTIGATION OF AMMONIA ADSORPTION ON FLY ASH DUE TO INSTALLATION OF SELECTIVE CATALYTIC REDUCTION SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    G.F. Brendel; J.E. Bonetti; R.F. Rathbone; R.N. Frey Jr.

    2000-11-01

    This report summarizes an investigation of the potential impacts associated with the utilization of selective catalytic reduction (SCR) systems at coal-fired power plants. The study was sponsored by the U.S. Department of Energy Emission Control By-Products Consortium, Dominion Generation, the University of Kentucky Center for Applied Energy Research and GAI Consultants, Inc. SCR systems are effective in reducing nitrogen oxides (NOx) emissions as required by the Clean Air Act (CAA) Amendments. However, there may be potential consequences associated with ammonia contamination of stack emissions and combustion by-products from these systems. Costs for air quality, landfill and pond environmental compliance may increase significantly and the marketability of ash may be seriously reduced, which, in turn, may also lead to increased disposal costs. The potential impacts to air, surface water, groundwater, ash disposal, ash utilization, health and safety, and environmental compliance can not be easily quantified based on the information presently available. The investigation included: (1) a review of information and data available from published and unpublished sources; (2) baseline ash characterization testing of ash samples produced from several central Appalachian high-volatile bituminous coals from plants that do not currently employ SCR systems in order to characterize the ash prior to ammonia exposure; (3) an investigation of ammonia release from fly ash, including leaching and thermal studies; and (4) an evaluation of the potential impacts on plant equipment, air quality, water quality, ash disposal operations, and ash marketing.

  7. Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

    Science.gov (United States)

    Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

    2018-04-01

    The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. Influence of basic properties of Mg,Al-mixed oxides on their catalytic activity in knoevenagel condensation between benzaldehyde and phenylsulfonylacetonitrile

    Directory of Open Access Journals (Sweden)

    Caridad Noda Pérez

    2009-01-01

    Full Text Available The catalytic performance of Mg,Al-mixed oxides (MO20, MO25 and MO33 derived from hydrotalcites was evaluated in the Knoevenagel reaction between benzaldehyde and phenylsulfonylacetonitrile at 373 and 383 K. The best results were obtained for the sample MO20 that presented the highest basic sites density and external area and the smallest crystallite sizes. The relative amount of basic sites with weak to intermediate strength also played an important role on catalytic performance. By increasing the catalyst content from 1 to 5 wt.% at 383 K, a complete conversion of the reactants is attained, producing α-phenylsulfonylcinnamonitrile with a selectivity of 100%.

  13. 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

  14. 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.

  15. Adaptive Model Predictive Control of Diesel Engine Selective Catalytic Reduction (SCR) Systems

    Science.gov (United States)

    McKinley, Thomas L.

    2009-01-01

    Selective catalytic reduction or SCR is coming into worldwide use for diesel engine emissions reduction for on- and off-highway vehicles. These applications are characterized by broad operating range as well as rapid and unpredictable changes in operating conditions. Significant nonlinearity, input and output constraints, and stringent performance…

  16. COMPARISON OF WEST GERMAN AND U.S. FLUE GAS DESULFURIZATION AND SELECTIVE CATALYTIC REDUCTION COSTS

    Science.gov (United States)

    The report documents a comparison of the actual cost retrofitting flue gas desulfurization (FGD) and selective catalytic reduction (SCR) on Federal Republic of German (FRG) boilers to cost estimating procedures used in the U.S. to estimate the retrofit of these controls on U.S. b...

  17. 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.

  18. Gold Supported on Graphene Oxide: An Active and Selective Catalyst for Phenylacetylene Hydrogenations at Low Temperatures

    DEFF Research Database (Denmark)

    Shao, Lidong; Huang, Xing; Teschner, Detre

    2014-01-01

    A constraint to industrial implementation of gold-catalyzed alkyne hydrogenation is that the catalytic activity was always inferior to those of other noble metals. In this work, gold was supported on graphene oxide (Au/GO) and used in a hydrogenation application. A 99% selectivity toward styrene...

  19. Improving catalytic selectivity through control of adsorption orientation

    Science.gov (United States)

    Pang, Simon H.

    In this thesis, we present an investigation, starting from surface science experiments, leading to design of supported catalysts, of how adsorption orientation can be used to affect reaction selectivity of highly functional molecules. The surface chemistry of furfuryl alcohol and benzyl alcohol and their respective aldehydes was studied on a Pd(111) single-crystal surface under ultra-high vacuum conditions. Temperature-programmed desorption experiments showed that synergistic chemistry existed between the aromatic ring and the oxygen-containing functional group, each allowing the other to participate in reaction pathways that a monofunctional molecule could not. Most important of these was a deoxygenation reaction that occurred more readily when the surface was crowded by the highest exposures. High-resolution electron energy loss spectroscopy revealed that at these high exposures, molecules were oriented upright on the surface, with the aromatic function extending into vacuum. In contrast, at low exposures, molecules were oriented flat on the surface. The upright adsorption geometry was correlated with deoxygenation, whereas the flat-lying geometry was correlated with decarbonylation. The insight gained from surface science experiments was utilized in catalyst design. Self-assembled monolayers of alkanethiolates were used to systematically reduce the average surface ensemble size, and the reaction selectivity was tracked. When a sparsely-packed monolayer was used, such as one formed by 1-adamantanethiol, the reactant furfural was still able to lie flat on the surface and the reaction selectivity was similar to that of the uncoated catalyst. However, when a densely-packed monolayer, formed by 1-octadecanethiol, was used, furfural was not able to adsorb flat on the surface and instead adopted an upright conformation, leading to a drastic increase in aldehyde hydrogenation and hydrodeoxygenation reaction selectivity. Using an even higher sulfur coverage from a

  20. [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.

  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. 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.

  3. 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....

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-15

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

  5. 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

  6. 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.

  7. Atmospheric oxidation of selected hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Olariu, R.I.

    2002-02-01

    This work presents investigations on the gas-phase chemistry of phenol and the cresol isomers performed in a 1080 l quartz glass reactor in Wuppertal and in a large-volume outdoor photoreactor EUPHORE in Valencia, Spain. The studies aimed at clarifying the oxidation mechanisms of the reactions of these compounds with OH and NO{sub 3} radicals. Product investigations on the oxidation of phenol and the cresol isomers initiated by OH radicals were performed in the 1080 l quartz glass reactor with analyses by in situ FT-IR absorption spectroscopy. The primary focus of the investigations was on the determination of product yields. This work represents the first determination and quantification of 1,2-dihydroxybenzenes in the OH oxidation of phenolic compounds. Possible reaction pathways leading to the observed products have been elucidated. (orig.)

  8. 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

  9. Selectivity of an Active Natural Zeolite in Catalytic Conversion Process of Bangkirai, Kruing and Kamper Woods Biofuel to Gasoline Fraction

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available The selectivity of an active natural zeolite (ZAAH in catalytic conversion process of Bangkirai, Kruing and Kamper woods biofuels has been studied. The ZAAH catalyst was prepared from a natural zeolite (ZA treated with acids solution (1% HF and 6M HCI and hydrothermal then calcined at 500 °C and oxidized at 400 °C under nitrogen and oxygen gas stream, respectively. Characterizations of the catalysts including Si/Al ratio and acidity were determined by atomic adsorption spectroscopy (AAS and ammonia gas adsorption method, respectively. The conversion process was carried out in a flow reactor system at 400 °C, under N2 stream (20 mL/min. The biofuel was vaporized from the pyrolysis zone to the catalytic reactor. A liquid product was covered and analyzed by gas chromatograph (GC and that connected with mass spectroscopy (GC-MS. The characterization results showed that the Si/AI ratio and acidity of the ZAAH were higher than that of the ZA catalyst. The GC-MS data showed that the highest product selectivity was 2,4-dimethyl heptane and 1,2-dimethyl benzene. The total product selectivity using the ZAAH catalyst (bangkirai = 68.10%; kruing = 54.76%; kamper = 50.72% was higher than that of the ZA catalyst (bangkirai = 39.24%; kruing = 44.38%; kamper = 46.11%.

  10. Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Housaindokht

    2013-01-01

    Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.

  11. 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.

  12. catalysed selective oxidation of benzyl alcohols using TEMPO and ...

    Indian Academy of Sciences (India)

    A general scheme for the oxidation of benzyl alcohols catalyzed by silica functionalized copper (II) has been designed. TEMPO, a free radical, assists this oxidation that was initiated by molecular oxygen which converts it to a primary oxidant. This catalytic combination i.e. SiO2 -Cu(II) in presence of TEMPO and oxygen ...

  13. Effect of selective catalytic reduction (SCR) on fine particle emission from two coal-fired power plants in China

    Science.gov (United States)

    Li, Zhen; Jiang, Jingkun; Ma, Zizhen; Wang, Shuxiao; Duan, Lei

    2015-11-01

    Nitrogen oxides (NOx) emission abatement of coal-fired power plants (CFPPs) requires large-scaled installation of selective catalytic reduction (SCR), which would reduce secondary fine particulate matter (PM2.5) (by reducing nitrate aerosol) in the atmosphere. However, our field measurement of two CFPPs equipped with SCR indicates a significant increase of SO42- and NH4+ emission in primary PM2.5, due to catalytic enhancement of SO2 oxidation to SO3 and introducing of NH3 as reducing agent. The subsequent formation of (NH4)2SO4 or NH4HSO4 aerosol is commonly concentrated in sub-micrometer particulate matter (PM1) with a bimodal pattern. The measurement at the inlet of stack also showed doubled primary PM2.5 emission by SCR operation. This effect should therefore be considered when updating emission inventory of CFPPs. By rough estimation, the enhanced primary PM2.5 emission from CFPPs by SCR operation would offset 12% of the ambient PM2.5 concentration reduction in cities as the benefit of national NOx emission abatement, which should draw attention of policy-makers for air pollution control.

  14. 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.

  15. 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

  16. Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

    Science.gov (United States)

    Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

    2017-06-14

    It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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)

  2. 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.

  3. 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 −}.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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)

  10. 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.

  11. 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)

  12. 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

  13. 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

  14. NOx Selective Catalytic Reduction (SCR) on Self-Supported V-W-doped TiO2 Nanofibers

    DEFF Research Database (Denmark)

    Marani, Debora; Silva, Rafael Hubert; Dankeaw, Apiwat

    2017-01-01

    Electrospun V–W–TiO2 catalysts, resulting in a solid solution of V and W in the anatase phase, are prepared as nonwoven nanofibers for NOx selective catalytic reduction (SCR). Preliminary catalytic characterization indicates their superior NOx conversion efficiency to the-state-of-the-art materia...

  15. Development of an azanoradamantane-type nitroxyl radical catalyst for class-selective oxidation of alcohols.

    Science.gov (United States)

    Doi, Ryusuke; Shibuya, Masatoshi; Murayama, Tsukasa; Yamamoto, Yoshihiko; Iwabuchi, Yoshiharu

    2015-01-02

    The development of 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO; 1,5-dimethyl-Nor-AZADO, 2) as an efficient catalyst for the selective oxidation of primary alcohols in the presence of secondary alcohols is described. The compact and rigid structure of the azanoradamantane nucleus confers potent catalytic ability to DMN-AZADO (2). A variety of hindered primary alcohols such as neopentyl primary alcohols were efficiently oxidized by DMN-AZADO (2) to the corresponding aldehydes, whereas secondary alcohols remained intact. DMN-AZADO (2) also has high catalytic efficiency for one-pot oxidation from primary alcohols to the corresponding carboxylic acids in the presence of secondary alcohols and for oxidative lactonization from diols.

  16. 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.

  17. 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.)

  18. 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.

  19. 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...

  20. Influence of peracetic acid modification on the physicochemical properties of activated carbon and its performance in the ozone-catalytic oxidation of gaseous benzene

    Science.gov (United States)

    Fang, Ruimei; Huang, Haibao; Huang, Wenjun; Ji, Jian; Feng, Qiuyu; Shu, Yajie; Zhan, Yujie; Liu, Gaoyuan; Xie, Ruijie

    2017-10-01

    Coal based activated carbon (AC) was pretreated by peracetic acid solution and used for supporting Mn catalyst towards oxidation of gaseous benzene by catalytic ozonation. The as-obtained activated carbon was characterized by XPS, BET, SEM, and TG technologies. It indicates that peracetic acid solution modification not only raised the quantity of chemisorbed oxygen or water, and hydroxyl group on activated carbon material surface, but also increased the specific surface area and benzene adsorption capacity of activated carbon. Benzene could be completely removed in 300 min and CO2 selectivity reached to 61.9% over Mn/AC-modified catalyst. A possible catalytic ozonation mechanism of activated carbon which was treated by peracetic acid solution supported Mn catalyst for oxidation of benzene was proposed.

  1. 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.

  2. 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.

  3. Formation of imines by selective gold-catalysed aerobic oxidative coupling of alcohols and amines under ambient conditions

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

    2010-01-01

    with excellent selectivity (above 98%) at moderate conversion under optimized conditions. The effect of catalytic amounts of different bases was studied, along with reaction temperature and time. Utilisation of a selective catalyst system that uses dioxygen as an oxidant and only produces water as by...

  4. 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.

  5. 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...

  6. 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

  7. NOx formation and selective non-catalytic reduction (SNCR) in a fluidized bed combustor of biomass

    International Nuclear Information System (INIS)

    Mahmoudi, Shiva; Baeyens, Jan; Seville, Jonathan P.K.

    2010-01-01

    Caledonian Paper (CaPa) is a major paper mill, located in Ayr, Scotland. For its steam supply, it previously relied on the use of a Circulating Fluidized Bed Combustor (CFBC) of 58 MW th , burning coal, wood bark and wastewater treatment sludge. It currently uses a bubbling fluidized bed combustor (BFBC) of 102 MW th to generate steam at 99 bar, superheated to 465 o C. The boiler is followed by steam turbines and a 15 kg/s steam circuit into the mill. Whereas previously coal, wood bark and wastewater treatment sludge were used as fuel, currently only plantation wood (mainly spruce), demolition wood, wood bark and sludge are used. Since these biosolids contain nitrogen, fuel NO x is formed at the combustion temperature of 850-900 o C. NO x emissions (NO + NO 2 ) vary on average between 300 and 600 mg/Nm 3 (dry gas). The current emission standard is 350 mg/Nm 3 but will be reduced in the future to a maximum of 233 mg/Nm 3 for stand-alone biomass combustors of capacity between 50 and 300 MW th according to the EU LCP standards. NO x abatement is therefore necessary. In the present paper we firstly review the NO x formation mechanisms, proving that for applications of fluidized bed combustion, fuel NO x is the main consideration, and the contribution of thermal NO x to the emissions insignificant. We then assess the deNO x techniques presented in the literature, with an updated review and special focus upon the techniques that are applicable at CaPa. From these techniques, Selective Non-catalytic Reduction (SNCR) using ammonia or urea emerges as the most appropriate NO x abatement solution. Although SNCR deNO x is a selective reduction, the reactions of NO x reduction by NH 3 in the presence of oxygen, and the oxidation of NH 3 proceed competitively. Both reactions were therefore studied in a lab-scale reactor and the results were transformed into design equations starting from the respective reaction kinetics. An overall deNO x yield can then be predicted for any

  8. Quinone-Catalyzed Selective Oxidation of Organic Molecules

    Science.gov (United States)

    Wendlandt, Alison E.

    2016-01-01

    Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili; Wickens, Zachary K.; Dong, Guangbin; Grubbs, Robert H.

    2012-01-01

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  17. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili

    2012-07-06

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  18. 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

  19. 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.

  20. 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...

  1. 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.

  2. Discovery of a selective catalytic p300/CBP inhibitor that targets lineage-specific tumours

    Energy Technology Data Exchange (ETDEWEB)

    Lasko, Loren M.; Jakob, Clarissa G.; Edalji, Rohinton P.; Qiu, Wei; Montgomery, Debra; Digiammarino, Enrico L.; Hansen, T. Matt; Risi, Roberto M.; Frey, Robin; Manaves, Vlasios; Shaw, Bailin; Algire, Mikkel; Hessler, Paul; Lam, Lloyd T.; Uziel, Tamar; Faivre, Emily; Ferguson, Debra; Buchanan, Fritz G.; Martin, Ruth L.; Torrent, Maricel; Chiang, Gary G.; Karukurichi, Kannan; Langston, J. William; Weinert, Brian T.; Choudhary, Chunaram; de Vries, Peter; Van Drie, John H.; McElligott, David; Kesicki, Ed; Marmorstein, Ronen; Sun, Chaohong; Cole, Philip A.; Rosenberg, Saul H.; Michaelides, Michael R.; Lai, Albert; Bromberg, Kenneth D. (AbbVie); (UCopenhagen); (Petra Pharma); (UPENN); (JHU); (Van Drie); (Faraday)

    2017-09-27

    The dynamic and reversible acetylation of proteins, catalysed by histone acetyltransferases (HATs) and histone deacetylases (HDACs), is a major epigenetic regulatory mechanism of gene transcription1 and is associated with multiple diseases. Histone deacetylase inhibitors are currently approved to treat certain cancers, but progress on the development of drug-like histone actyltransferase inhibitors has lagged behind2. The histone acetyltransferase paralogues p300 and CREB-binding protein (CBP) are key transcriptional co-activators that are essential for a multitude of cellular processes, and have also been implicated in human pathological conditions (including cancer3). Current inhibitors of the p300 and CBP histone acetyltransferase domains, including natural products4, bi-substrate analogues5 and the widely used small molecule C6466,7, lack potency or selectivity. Here, we describe A-485, a potent, selective and drug-like catalytic inhibitor of p300 and CBP. We present a high resolution (1.95 Å) co-crystal structure of a small molecule bound to the catalytic active site of p300 and demonstrate that A-485 competes with acetyl coenzyme A (acetyl-CoA). A-485 selectively inhibited proliferation in lineage-specific tumour types, including several haematological malignancies and androgen receptor-positive prostate cancer. A-485 inhibited the androgen receptor transcriptional program in both androgen-sensitive and castration-resistant prostate cancer and inhibited tumour growth in a castration-resistant xenograft model. These results demonstrate the feasibility of using small molecule inhibitors to selectively target the catalytic activity of histone acetyltransferases, which may provide effective treatments for transcriptional activator-driven malignancies and diseases.

  3. 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

  4. 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.

  5. 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%

  6. Size-Selective Oxidation of Aldehydes with Zeolite Encapsulated Gold Nanoparticles

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane; Laursen, Anders Bo; Kegnæs, Søren

    2011-01-01

    Here, we report a synthesis and catalytic study of hybrid materials comprised of 1–3 nm sinter-stable Au nanoparticles in MFI-type zeolites. An optional post-treatment in aqua regia effectively remove Au from the external surfaces. The size-selective aerobic aldehyde oxidation verifies that the a......Here, we report a synthesis and catalytic study of hybrid materials comprised of 1–3 nm sinter-stable Au nanoparticles in MFI-type zeolites. An optional post-treatment in aqua regia effectively remove Au from the external surfaces. The size-selective aerobic aldehyde oxidation verifies...... that the active Au is accessible only through the zeolite micropores....

  7. Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

    Science.gov (United States)

    Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

    2018-05-01

    A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

  8. 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.

  9. 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.

  10. Selective catalytic reduction system and process using a pre-sulfated zirconia binder

    Science.gov (United States)

    Sobolevskiy, Anatoly; Rossin, Joseph A.

    2010-06-29

    A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

  11. HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES; FINAL

    International Nuclear Information System (INIS)

    Jerry B. Urbas

    1999-01-01

    The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO(sub x) control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO(sub x) while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO(sub x) reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO(sub x) reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO(sub x) emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO(sub x) reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm(sup 3) (8 ppm) at the catalyst inlet. After resolving the stratification problem

  12. HYBRID SELECTIVE NON-CATALYTIC REDUCTION (SNCR)/SELECTIVE CATALYTIC REDUCTION (SCR) DEMONSTRATION FOR THE REMOVAL OF NOx FROM BOILER FLUE GASES

    Energy Technology Data Exchange (ETDEWEB)

    Jerry B. Urbas

    1999-05-01

    The U. S. Department of Energy (DOE), Electric Power Research Institute (EPRI), Pennsylvania Electric Energy Research Council, (PEERC), New York State Electric and Gas and GPU Generation, Inc. jointly funded a demonstration to determine the capabilities for Hybrid SNCR/SCR (Selective Non-Catalytic Reduction/Selective Catalytic Reduction) technology. The demonstration site was GPU Generation's Seward Unit No.5 (147MW) located in Seward Pennsylvania. The demonstration began in October of 1997 and ended in December 1998. DOE funding was provided through Grant No. DE-FG22-96PC96256 with T. J. Feeley as the Project Manager. EPRI funding was provided through agreements TC4599-001-26999 and TC4599-002-26999 with E. Hughes as the Project Manager. This project demonstrated the operation of the Hybrid SNCR/SCR NO{sub x} control process on a full-scale coal fired utility boiler. The hybrid technology was expected to provide a cost-effective method of reducing NO{sub x} while balancing capital and operation costs. An existing urea based SNCR system was modified with an expanded-duct catalyst to provide increased NO{sub x} reduction efficiency from the SNCR while producing increased ammonia slip levels to the catalyst. The catalyst was sized to reduce the ammonia slip to the air heaters to less than 2 ppm while providing equivalent NO{sub x} reductions. The project goals were to demonstrate hybrid technology is capable of achieving at least a 55% reduction in NO{sub x} emissions while maintaining less than 2ppm ammonia slip to the air heaters, maintain flyash marketability, verify the cost benefit and applicability of Hybrid post combustion technology, and reduce forced outages due to ammonium bisulfate (ABS) fouling of the air heaters. Early system limitations, due to gas temperature stratification, restricted the Hybrid NO{sub x} reduction capabilities to 48% with an ammonia slip of 6.1 mg/Nm{sup 3} (8 ppm) at the catalyst inlet. After resolving the stratification

  13. 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.

  14. 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.

  15. Activity and selectivity of manganese oxides in alcohols Conversion as influenced by gamma-irradiation

    International Nuclear Information System (INIS)

    Doheim, M.M.; Ahmed, A.S.; El-Shobaky, G.A.

    2002-01-01

    Manganese oxide samples obtained from thermal decomposition of manganese carbonate at 400 and 600 deg C were subjected to different doses of g-irradiation within the range 0.2 to 1.6 MGy. The surface and catalytic properties of the above samples were studied using nitrogen adsorption isotherms measured at -196 deg C and catalytic conversion of ethanol and isopropanol at 300-400 deg C using micropulse technique. The results obtained revealed that manganese oxides obtained at 400 deg C consisted of a mixture of Mn 2 O 3 and MnO 2 while the samples calcined at 600 deg C composed entirely of Mn 2 O 3 . Gamma-irradiation resulted in a decrease in the particle size of manganese oxide phases with subsequent increase in their specific surface areas. Gamma-irradiation with 0.2 and 0.8 MGy effected a measurable progressive decrease in the catalytic activity in dehydration and dehydrogenation of both alcohols. However, the treated catalyst retained their initial activity upon exposure to a dose of 1.6 MGy. Also, g-irradiation increased the selectivities of the investigated solids towards dehydrogenation of both alcohols. The catalyst samples precalcined at 600 deg C exhibited higher catalytic activities than those precalcined at 400 deg C. (author)

  16. Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

    Science.gov (United States)

    Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

    2016-06-20

    The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 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.

  18. 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.

  19. 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)

  20. 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.

  1. 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.

  2. 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...

  3. 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.

  4. 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.

  5. 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

  6. 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.)

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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)

  16. 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.

  17. 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.

  18. Zeolite-Y entrapped Ru(III and Fe(III complexes as heterogeneous catalysts for catalytic oxidation of cyclohexane reaction

    Directory of Open Access Journals (Sweden)

    Chetan K. Modi

    2017-02-01

    Full Text Available Catalysis is probably one of the greatest contributions of chemistry to both economic growth and environmental protection. Herein we report the catalytic behavior of zeolite-Y entrapped Ru(III and Fe(III complexes with general formulae [M(VTCH2·2H2O]+-Y and [M(VFCH2·2H2O]+-Y [where, VTCH = vanillin thiophene-2-carboxylic hydrazone and VFCH = vanillin furoic-2-carboxylic hydrazone] over the oxidation of cyclohexane forming cyclohexanone and cyclohexanol. The samples were corroborated by various physico-chemical techniques. These zeolite-Y based complexes are stable and recyclable under current reaction conditions. Amongst them, [Ru(VTCH2⋅2H2O]+-Y showed higher catalytic activity (41.1% with cyclohexanone (84.6% selectivity.

  19. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

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

  20. Selectivity of Catalytically Modified Tin Dioxide to CO and NH3 Gas Mixtures

    Directory of Open Access Journals (Sweden)

    Artem Marikutsa

    2015-10-01

    Full Text Available This paper is aimed at selectivity investigation of gas sensors, based on chemically modified nanocrystalline tin dioxide in the detection of CO and ammonia mixtures in air. Sol-gel prepared tin dioxide was modified by palladium and ruthenium oxides clusters via an impregnation technique. Sensing behavior to CO, NH3 and their mixtures in air was studied by in situ resistance measurements. Using the appropriate match of operating temperatures, it was shown that the reducing gases mixed in a ppm-level with air could be discriminated by the noble metal oxide-modified SnO2. Introducing palladium oxide provided high CO-sensitivity at 25–50 °C. Tin dioxide modified by ruthenium oxide demonstrated increased sensor signals to ammonia at 150–200 °C, and selectivity to NH3 in presence of higher CO concentrations.

  1. 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

  2. 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.

  3. Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

    Science.gov (United States)

    Alotaibi, Mohammed T.; Taylor, Martin J.; Liu, Dan; Beaumont, Simon K.; Kyriakou, Georgios

    2016-04-01

    Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 ± 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 °C. The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nanoparticles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith.

  4. 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.

  5. 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.

  6. Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields

    KAUST Repository

    Zhang, Jizhe

    2014-09-01

    Direct conversion of raw biomass materials to fine chemicals is of great significance from both economic and ecological perspectives. In this paper, we report that a Keggin-type vanadium-substituted phosphomolybdic acid catalyst, namely H4PVMo11O40, is capable of converting various biomass-derived substrates to formic acid and acetic acid with high selectivity in a water medium and oxygen atmosphere. Under optimized reaction conditions, H4PVMo11O40 gave an exceptionally high yield of formic acid (67.8%) from cellulose, far exceeding the values achieved in previous catalytic systems. Our study demonstrates that heteropoly acids are generally effective catalysts for biomass conversion due to their strong acidities, whereas the composition of metal addenda atoms in the catalysts has crucial influence on the reaction pathway and the product selectivity. © 2013 Elsevier B.V.

  7. Experimental Determination and Modeling of the Phase Behavior for the Selective Oxidation of Benzyl Alcohol in Supercritical CO2

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Beier, Matthias Josef; Grunwaldt, Jan-Dierk

    2011-01-01

    In this study the phase behavior of mixtures relevant to the selective catalytic oxidation of benzyl alcohol to benzaldehyde by molecular oxygen in supercritical CO2 is investigated. Initially, the solubility of N2 in benzaldehyde as well as the dew points of CO2–benzyl alcohol–O2 and CO2...

  8. LASER INDUCED SELECTIVE ACTIVATION UTILIZING AUTO-CATALYTIC ELECTROLESS PLATING ON POLYMER SURFACE

    DEFF Research Database (Denmark)

    Zhang, Yang; Nielsen, Jakob Skov; Tang, Peter Torben

    2009-01-01

    . Characterization of the deposited copper layer was used to select and improve laser parameters. Several types of polymers with different melting points were used as substrate. Using the above mentioned laser treatment, standard grades of thermoplastic materials such as ABS, SAN, PE, PC and others have been......This paper presents a new method for selective micro metallization of polymers induced by laser. An Nd: YAG laser was employed to draw patterns on polymer surfaces using a special set-up. After subsequent activation and auto-catalytic electroless plating, copper only deposited on the laser tracks....... Induced by the laser, porous and rough structures are formed on the surface, which favours the palladium attachment during the activation step prior to the metallization. Laser focus detection, scanning electron microscopy (SEM) and other instruments were used to analyze the topography of the laser track...

  9. 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.

  10. 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…

  11. 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

  12. Niobium(V) saponite clay for the catalytic oxidative abatement of chemical warfare agents.

    Science.gov (United States)

    Carniato, Fabio; Bisio, Chiara; Psaro, Rinaldo; Marchese, Leonardo; Guidotti, Matteo

    2014-09-15

    A Nb(V)-containing saponite clay was designed to selectively transform toxic organosulfur chemical warfare agents (CWAs) under extremely mild conditions into nontoxic products with reduced environmental impact. Thanks to the insertion of Nb(V) sites within the saponite framework, a bifunctional catalyst with strong oxidizing and acid properties was obtained. Remarkable activity and high selectivity were observed for the oxidative abatement of (2-chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature with aqueous hydrogen peroxide. This performance was significantly better compared to a conventional commercial decontamination powder. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst; Oxidacion catalitica de albendazol empleando como catalizador molibdeno soportado en nanotubos de carbono

    Energy Technology Data Exchange (ETDEWEB)

    Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R., E-mail: msun@pucp.edu.pe [Departamento de Ciencias, Seccion Quimica. Pontificia Universidad Catolica del Peru, Avenida Universitaria 1801, Lima (Peru); Picasso Escobar, Gino I. [Laboratorio de Investigacion de Fisicoquimica, Facultad de Ciencias, Universidad Nacional de Ingenieria, Avenida Tupac Amaru 210, Lima (Peru)

    2013-10-15

    The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C{sub 12}H{sub 15}N{sub 3}O{sub 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 {sup o}C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H{sub 2}NCONH{sub 2}·H{sub 2}O{sub 2}) as oxidizing agent and methanol (CH{sub 3}OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N{sub 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)

  14. 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

  15. 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

  16. 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

  17. 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

  18. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    International Nuclear Information System (INIS)

    Sarah C. Larson; Vicki H. Grassian

    2006-01-01

    Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO x ) and ammonia (NH 3 ) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO 2 was observed at room temperature in the presence of NH 3 as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO 2 reduction with NH 3 relative to nanocrystalline NaY

  19. 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

  20. 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.

  1. 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

  2. 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.)

  3. 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

  4. 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.

  5. 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.

  6. Catalytic oxidation of chlorinated volatile organic compounds, dichloromethane and perchloroethylene. New knowledge for the industrial CVOC emission abatement

    Energy Technology Data Exchange (ETDEWEB)

    Pitkaeaho, S.

    2013-09-01

    The releases of chlorinated volatile organic compounds (CVOCs) are controlled by strict regulations setting high demands for the abatement systems. Low temperature catalytic oxidation is a viable technology to economically destroy these often refractory emissions. Catalysts applied in the oxidation of CVOCs should be highly active and selective but also maintain a high resistance towards deactivation. In this study, a total of 33 different {gamma}-Al{sub 2}O{sub 3} containing metallic monoliths were studied in dichloromethane (DCM) and 25 of them in perchloroethylene (PCE) oxidation. The active compounds used were Pt, Pd, Rh or V{sub 2}O{sub 5} alone or as mixtures. The catalysts were divided into three different testing sets: industrial, CVOC and research catalysts. ICP-OES, physisorption, chemisorption, XRD, UV-vis DRS, isotopic oxygen exchange, IC, NH{sub 3}-TPD, H{sub 2}-TPR and FESEM-EDS were used to characterise the catalysts. Screening of the industrial catalysts revealed that the addition of V{sub 2}O{sub 5} improved the performance of the catalyst. DCM abatement was easily affected by the addition of VOC or water, but the effect on the PCE oxidation was only minor. Based on these screening tests, a set of CVOC catalysts were developed and installed into an industrial incinerator. The comparison between the laboratory and industrial scale studies showed that DCM oxidation in an industrial incinerator could be predicted relatively well. Instead, PCE was always seen to be oxidised far better in an industrial unit indicating that the transient oxidation conditions are beneficial for the PCE oxidation. Before starting the experiments with research catalysts, the water feed was optimised to 1.5 wt.%. Besides enhancing the HCl yields, water improved the DCM and PCE conversions. In the absence of oxygen, i.e. during destructive adsorption, the presence of water was seen to have an even more pronounced effect on the HCl formation and on the catalysts

  7. Selective Catalytic Reduction (SCR) for mobile application - heavy duty diesel; Selektive Katalytische Reduktion (SCR) fuer die mobile Anwendung - LKW

    Energy Technology Data Exchange (ETDEWEB)

    Huennekes, E.; Neubauer, T. [Engelhard Technologies GmbH, Hannover (Germany); Roth, S.A.; Patchett, J.A. [Engelhard Corp., R and D, Iselin, NJ (United States)

    2006-07-01

    Different system configurations of particulate and NOx control via selective catalytic reduction (SCR) were discussed. Advantages and disadvantages were described and the final choice of the optimum system will strongly depend on the application, the market (US, EU) and the system costs. Especially when considering low temperature NOx control, the optimum adjustment of the NO{sub 2}/NO{sub x} ratio in front of an SCR system plays an important role. When generating NO2 over an oxidation catalyst, the resulting NO{sub 2}/NO{sub x} ratio strongly depends on temperature and space velocity. Steady state data show an optimum NO{sub 2}/NO{sub x} ratio between 35 and 60% at temperatures about 240 C. Three DOC systems in front of an SCR system were investigated with the purpose to generate high, low and optimum NO{sub 2}/NO{sub x} ratios. The fast SCR reaction at 1:1 NO: NO2 with NH{sub 3} is the preferred reaction pathway until either NO or NO{sub 2} are consumed. The benefit of an optimum designed DOC system can be seen in the transient response after a sudden increase in urea dosing. The time for the optimum designed system to reach maximum NO{sub x} conversion is much shorter compared with systems having excess NO or NO{sub 2} Ammonia oxidation catalysts (AMOX) are effective means in controlling ammonia from SCR systems. To be effective, AMOX must have selectivity to nitrogen over N{sub 2}O and NO{sub x}. (orig.)

  8. 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.

  9. 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

  10. How Gold Deposition Affects Anatase Performance in the Photo-catalytic Oxidation of Cyclohexane

    NARCIS (Netherlands)

    Carneiro, J.T.; Carneiro, Joana T.; Yang, Chieh-Chao; Moma, John A.; Moulijn, Jacob A.; Mul, Guido

    2009-01-01

    Gold deposition on Hombikat UV100 was found to negatively affect the activity of this Anatase catalyst in selective photo-oxidation of cyclohexane. By ammonia TPD and DRIFT spectroscopy it was determined that the Au deposition procedure leads to a significant decrease in OH-group density (mol m−2

  11. Synthesis, structural characterization and selectively catalytic properties of metal-organic frameworks with nano-sized channels: A modular design strategy

    International Nuclear Information System (INIS)

    Qiu Lingguang; Gu Lina; Hu Gang; Zhang Lide

    2009-01-01

    Modular design method for designing and synthesizing microporous metal-organic frameworks (MOFs) with selective catalytical activity was described. MOFs with both nano-sized channels and potential catalytic activities could be obtained through self-assembly of a framework unit and a catalyst unit. By selecting hexaaquo metal complexes and the ligand BTC (BTC=1,3,5-benzenetricarboxylate) as framework-building blocks and using the metal complex [M(phen) 2 (H 2 O) 2 ] 2+ (phen=1,10-phenanthroline) as a catalyst unit, a series of supramolecular MOFs 1-7 with three-dimensional nano-sized channels, i.e. [M 1 (H 2 O) 6 ].[M 2 (phen) 2 (H 2 O) 2 ] 2 .2(BTC).xH 2 O (M 1 , M 2 =Co(II), Ni(II), Cu(II), Zn(II), or Mn(II), phen=1,10-phenanthroline, BTC=1,3,5-benzenetricarboxylate, x=22-24), were synthesized through self-assembly, and their structures were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. These supramolecular microporous MOFs showed significant size and shape selectivity in the catalyzed oxidation of phenols, which is due to catalytic reactions taking place in the channels of the framework. Design strategy, synthesis, and self-assembly mechanism for the construction of these porous MOFs were discussed. - Grapical abstract: A modular design strategy has been developed to synthesize microporous metal-organic frameworks with potential catalytic activity by self-assembly of the framework-building blocks and the catalyst unit

  12. Selective catalytic reduction (SCR) NOx control for small natural gas-fired prime movers

    International Nuclear Information System (INIS)

    Shareef, G.S.; Stone, D.K.; Ferry, K.R.; Johnson, K.L.; Locke, K.S.

    1992-01-01

    The application of selective catalytic reduction (SCR) to small natural gas-fired prime movers at cogeneration facilities and compressor stations could possibly increase due to regulatory forces to limit NO x from such sources. The natural gas industry is presently without a current database with which to evaluate the cost and operating characteristics of SCR under the conditions anticipated for small prime movers. This paper presents the results from a two-phase study undertaken to document SCR applications with emphasis on SCR system performance and costs. The database of small natural gas-fired prime mover SCR experience, focusing on prime mover characterization, SCR system performance, and SCR system costs will be described. Result from analysis of performance and cost data will be discussed, including analytical tools developed to project SCR system performance and costs

  13. Selective catalytic oxidation of NO as a process stage in NOx separation from power plant and production systems off-gases. Catalyst development and reaction kinetics. Final report. Die selektive katalytische Oxidation des NO als Prozess-Stufe bei der Stickoxidabscheidung aus Abgasen von Kraftwerken und Produktionsanlagen. Katalysatorentwicklung und Reaktionskinetik. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Seifert, J.

    1989-06-01

    The research project was to investigate the heterogeneously catalyzed oxidation of NO in flue gas using 1. metal oxide catalysts (commonly on a MnO{sub 2} basis), 2. ZSM5 zeolites (pentasil), and 3. noble metal catalysts. Apart from the reaction kinetics, also the activity and resistance to typical catalyst poisons (SO{sub 2}, HCl, HF, heavy metals) were investigated. A fully automatic, computer-controlled experimental apparatus was developed which apart from the analysis of reaction products permitted also dynamic experiments with time constants in the seconds range and experiments with cyclic variation of concentration, temperature, and time of residue. (RB).

  14. Application of near ambient pressure gas-phase X-ray photoelectron spectroscopy to the investigation of catalytic properties of copper in methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Prosvirin, Igor P., E-mail: prosvirin@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Bukhtiyarov, Andrey V., E-mail: avb@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva ave. 5, 630090 Novosibirsk (Russian Federation); Research and Educational Center for Energy Efficient Catalysis, Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Bluhm, Hendrik, E-mail: hbluhm@lbl.gov [Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720 (United States); Bukhtiyarov, Valerii I., E-mail: vib@catalysis.ru [Boreskov Institute of Catalysis, Lavrentieva ave. 5, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation); Research and Educational Center for Energy Efficient Catalysis, Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk (Russian Federation)

    2016-02-15

    Graphical abstract: - Highlights: • Selective oxidation of CH{sub 3}OH to CH{sub 2}O over a Cu foil has been studied by in situ gas phase XPS. • C1s and O1s spectra were used for identification of reagents and reaction products in a gas phase. • Catalytic data (conversions and reaction products yields) calculated from XPS spectra are in a good agreement with QMS results. • The possible reasons of the observed variations in reaction mechanism have been discussed. - Abstract: Application of near ambient pressure (NAP) X-ray photoelectron spectroscopy for characterization of catalytic properties of a heterogeneous catalyst through measurement and analysis of the core-level spectra from gas phase constituents, which become measurable in submillibar pressure range, has been demonstrated for the reaction of methanol oxidation over polycrystalline copper foil. To improve the accuracy of quantitative analysis of the gas phase signals for the routine XPS spectrometer with double Al/Mg anode used in these experiments, the sample was removed from XPS analysis zone, but it was still located in high-pressure gas cell. As consequence, only gas phase peaks from reagents and reaction products have been observed in XPS spectra. Quantitative analysis of the spectra has allowed us to calculate conversions of the reagents and yields of the reaction products, or, other words, to characterize the catalytic properties of the catalyst and to track their changes with temperature. Further comparison of the catalytic properties with concentration of the surface species measured by in situ XPS in separate experiments, but under the same conditions, gives a possibility to discuss the reaction mechanisms.

  15. 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

  16. 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.

  17. 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

  18. 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....

  19. Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.A.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    Ethene production is one of the most important transformations in chemical industry, given that C{sub 2}H{sub 4} serves as building block for many mass-market products. Besides conventional thermal processes like steam cracking of ethane, ethane can be produced selectively by catalytic processes. One of the classes of catalysts that have been reported in literature as active and highly selective for the oxidative dehydrogenation of ethane is that of supported molten chloride catalysts, containing an alkali chloride overlayer on a solid support. This work deals with fundamental aspects of the catalytic action in latter class of catalysts. Results from kinetic reaction studies are related to observations in detailed characterization and lead to a comprehensive mechanistic understanding. Of fundamental importance towards mechanistic insights is the oxygen storage capacity of the catalysts that has been determined by transient step experiments. (orig.)

  20. 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.

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

    Science.gov (United States)

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

    2010-05-01

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

  2. Validation of the catalytic properties of Cu-Os/13X using single fixed bed reactor in selective catalytic reduction of NO

    International Nuclear Information System (INIS)

    Oh, Kwang Seok; Woo, Seong Ihl

    2007-01-01

    Catalytic decomposition of NO over Cu-Os/13X has been carried out in a tubular fixed bed reactor at atmospheric pressure and the results were compared with literature data performed by high-throughput screening (HTS). The activity and durability of Cu-Os/13X prepared by conventional ion-exchange method have been investigated in the presence of H 2 O and SO 2 . It was found that Cu-Os/13X prepared by ion-exchange shows a high activity in a wide temperature range in selective catalytic reduction (SCR) of NO with C 3 H 6 compared to Cu/13X, proving the existence of more NO adsorption site on Cu-Os/13X. However, Cu-Os/13X exhibited low activity in the presence of water, and was quite different from the result reported in literature. SO 2 resistance is also low and does not recover its original activity when the SO 2 was blocked in the feed gas stream. This result suggested that catalytic activity between combinatorial screening and conventional testing should be compared to confirm the validity of high-throughput screening

  3. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NOx with NH₃ at low temperature.

    Science.gov (United States)

    Wang, Peng; Sun, Hong; Quan, Xie; Chen, Shuo

    2016-01-15

    The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO2 and H2O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO2/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NOx conversion ranges from 196 to 300°C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO2 species responsible for fast SCR reactions. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Real-world exhaust temperature profiles of on-road heavy-duty diesel vehicles equipped with selective catalytic reduction.

    Science.gov (United States)

    Boriboonsomsin, Kanok; Durbin, Thomas; Scora, George; Johnson, Kent; Sandez, Daniel; Vu, Alexander; Jiang, Yu; Burnette, Andrew; Yoon, Seungju; Collins, John; Dai, Zhen; Fulper, Carl; Kishan, Sandeep; Sabisch, Michael; Jackson, Doug

    2018-09-01

    On-road heavy-duty diesel vehicles are a major contributor of oxides of nitrogen (NO x ) emissions. In the US, many heavy-duty diesel vehicles employ selective catalytic reduction (SCR) technology to meet the 2010 emission standard for NO x . Typically, SCR needs to be at least 200°C before a significant level of NO x reduction is achieved. However, this SCR temperature requirement may not be met under some real-world operating conditions, such as during cold starts, long idling, or low speed/low engine load driving activities. The frequency of vehicle operation with low SCR temperature varies partly by the vehicle's vocational use. In this study, detailed vehicle and engine activity data were collected from 90 heavy-duty vehicles involved in a range of vocations, including line haul, drayage, construction, agricultural, food distribution, beverage distribution, refuse, public work, and utility repair. The data were used to create real-world SCR temperature and engine load profiles and identify the fraction of vehicle operating time that SCR may not be as effective for NO x control. It is found that the vehicles participated in this study operate with SCR temperature lower than 200°C for 11-70% of the time depending on their vocation type. This implies that real-world NO x control efficiency could deviate from the control efficiency observed during engine certification. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. 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.

  6. [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.

  7. Microwave-irradiated preparation of reduced graphene oxide-Ni nanostructures and their enhanced performance for catalytic reduction of 4-nitrophenol

    International Nuclear Information System (INIS)

    Qiu, Hanxun; Qiu, Feilong; Han, Xuebin; Li, Jing; Yang, Junhe

    2017-01-01

    Highlights: • Nickel nanoparticle-decorated reduced graphene-oxide nanostructures were prepared by an environmentally friendly, one-pot strategy via an efficient microwave irradiation approach. • Upon microwave irradiation, the composites could be prepared within only a few hundred seconds, much faster than using the widely used traditional hydrothermal methods that may take tens of hours generally. • The nanostructure exhibits superior catalytic activity and selectivity towards transforming the highly toxic nitroaromatic compounds to industrially useful intermediates • The corresponding kinetic reaction rate constant (κ) is even four-fold compared to pure Ni nanoparticles. - Abstract: Here we report an environmentally friendly, one-pot strategy toward preparation of nickel nanoparticle-decorated reduced graphene-oxide (Ni-RGO) nanostructures, by employing Ni(AC) 2 as nickel source and ethylene glycol as both solvent and reducing agent via a facile microwave irradiation heating approach. The results show that Ni nanoparticles with an average diameter of around 40 nm are homogeneously anchored onto the surface of RGO sheets. As compared to the pure Ni nanoparticles and RGO sheets, Ni-RGO composites with over 64 wt% loading of Ni nanoparticles possess superior catalytic activities and selectivity toward the reduction of 4-nitrophenol. The corresponding kinetic reaction rate constant (defined as κ) is even four-fold compared to pure Ni nanoparticles. Such promising composites show great potential for friendly treatment of industrial waste containing nitrophenol in a simple, sustainable and green way.

  8. Microwave-irradiated preparation of reduced graphene oxide-Ni nanostructures and their enhanced performance for catalytic reduction of 4-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Hanxun, E-mail: hxqiu@usst.edu.cn; Qiu, Feilong; Han, Xuebin; Li, Jing; Yang, Junhe, E-mail: jhyang@usst.edu.cn

    2017-06-15

    Highlights: • Nickel nanoparticle-decorated reduced graphene-oxide nanostructures were prepared by an environmentally friendly, one-pot strategy via an efficient microwave irradiation approach. • Upon microwave irradiation, the composites could be prepared within only a few hundred seconds, much faster than using the widely used traditional hydrothermal methods that may take tens of hours generally. • The nanostructure exhibits superior catalytic activity and selectivity towards transforming the highly toxic nitroaromatic compounds to industrially useful intermediates • The corresponding kinetic reaction rate constant (κ) is even four-fold compared to pure Ni nanoparticles. - Abstract: Here we report an environmentally friendly, one-pot strategy toward preparation of nickel nanoparticle-decorated reduced graphene-oxide (Ni-RGO) nanostructures, by employing Ni(AC){sub 2} as nickel source and ethylene glycol as both solvent and reducing agent via a facile microwave irradiation heating approach. The results show that Ni nanoparticles with an average diameter of around 40 nm are homogeneously anchored onto the surface of RGO sheets. As compared to the pure Ni nanoparticles and RGO sheets, Ni-RGO composites with over 64 wt% loading of Ni nanoparticles possess superior catalytic activities and selectivity toward the reduction of 4-nitrophenol. The corresponding kinetic reaction rate constant (defined as κ) is even four-fold compared to pure Ni nanoparticles. Such promising composites show great potential for friendly treatment of industrial waste containing nitrophenol in a simple, sustainable and green way.

  9. Selective electrocatalysis of biofuel molecular oxidation using palladium nanoparticles generated on Shewanella oneidensis MR-1

    DEFF Research Database (Denmark)

    Wu, Ranran; Tian, Xiaochun; Xiao, Yong

    2018-01-01

    of formate with 200 mV less over-potential. Notably they show unique selective activity toward electrochemical oxidation of formate, whereas no electrochemical catalysis was found for oxidation of ethanol, methanol and acetate. This work demonstrates a sustainable and low-cost method for producing efficient......Production of molecular scale palladium (Pd) nanoparticles (NPs) is important due to their catalytic function in electrochemical oxidation of a number of core fuel molecules in fuel cells. Biogenic methods offer an economic and environmentally friendly synthesis route. In this work...... membrane surface. Mapping by conductive atomic force microscopy shows that the presence of these PdNPs promotes electron transfer and enhances the electric conductivity of the cells. Compared to electrodeposited PdNPs, PdNPs generated by S. oneidensis MR-1 catalyze electrochemically the oxidation...

  10. 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.

  11. Systematic study on the influence of the morphology of α-MoO3 in the selective oxidation of propylene

    DEFF Research Database (Denmark)

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

    2015-01-01

    A variety of morphologically different α-MoO3 samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO3 prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from...... with nitric acid at 180°C. Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550°C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization...... studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion....

  12. Effects of Particle Filters and Selective Catalytic Reduction on In-Use Heavy-Duty Diesel Truck Emissions

    Science.gov (United States)

    Preble, C.; Cados, T.; Harley, R.; Kirchstetter, T.

    2016-12-01

    Heavy-duty diesel trucks (HDDT) are a major source of nitrogen oxides (NOx) and black carbon (BC) in urban environments, contributing to persistent ozone and particulate matter air quality problems. Diesel particle filters (DPFs) and selective catalytic reduction (SCR) systems that target PM and NOx emissions, respectively, have recently become standard equipment on new HDDT. DPFs can also be installed on older engines as a retrofit device. Previous work has shown that DPF and SCR systems can reduce NOx and BC emissions by up to 70% and 90%, respectively, compared to modern trucks without these after-treatment controls (Preble et al., ES&T 2015). DPFs can have the undesirable side-effect of increasing ultrafine particle (UFP) and nitrogen dioxide (NO2) emissions. While SCR systems can partially mitigate DPF-related NO2 increases, these systems can emit nitrous oxide (N2O), a potent greenhouse gas. We report new results from a study of HDDT emissions conducted in fall 2015 at the Port of Oakland and Caldecott Tunnel in California's San Francisco Bay Area. We report pollutant emission factors (g kg-1) for emitted NOx, NO2, BC, PM2.5, UFP, and N2O on a truck-by-truck basis. Using a roadside license plate recognition system, we categorize each truck by its engine model year and installed after-treatment controls. From this, we develop emissions profiles for trucks with and without DPF and SCR. We evaluate the effectiveness of these devices as a function of their age to determine whether degradation is an issue. We also compare the emission profiles of trucks traveling at low speeds along a level, arterial road en route to the port and at high speeds up a 4% grade highway approaching the tunnel. Given the climate impacts of BC and N2O, we also examine the global warming potential of emissions from trucks with and without DPF and SCR.

  13. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction

    International Nuclear Information System (INIS)

    Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A.; García, Juan

    2013-01-01

    Highlights: ► Ni supported over hydrotalcite calcined precursors as catalyst. ► Catalytic wet air oxidation in trickle bed reactor for Chromotrope 2R removal. ► Dye removal depends on temperature, initial dye concentration and flow rate. ► The catalyst proved to bare-usable after in situ regeneration. -- Abstract: Active nickel catalysts (7 wt%) supported over Mg–Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min −1 and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min −1 , respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T r = 0.098 g Ni min mL −1 . After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T r = 0.098 g Ni min mL −1 , attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity

  14. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction

    Energy Technology Data Exchange (ETDEWEB)

    Vallet, Ana [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Ovejero, Gabriel, E-mail: govejero@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Rodríguez, Araceli [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain); Peres, José A. [Centro de Química de Vila Real, Universidade de Trás-os-Montes e Alto Douro, Apartado 1013, 5001-801 Vila Real (Portugal); García, Juan, E-mail: juangcia@quim.ucm.es [Grupo de Catálisis y Procesos de Separación (CyPS), Departamento de Ingeniería Química, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid (Spain)

    2013-01-15

    Highlights: ► Ni supported over hydrotalcite calcined precursors as catalyst. ► Catalytic wet air oxidation in trickle bed reactor for Chromotrope 2R removal. ► Dye removal depends on temperature, initial dye concentration and flow rate. ► The catalyst proved to bare-usable after in situ regeneration. -- Abstract: Active nickel catalysts (7 wt%) supported over Mg–Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min{sup −1} and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min{sup −1}, respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T{sub r} = 0.098 g{sub Ni} min mL{sup −1}. After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T{sub r} = 0.098 g{sub Ni} min mL{sup −1}, attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity.

  15. 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

  16. 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)

  17. 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.

  18. 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.

  19. 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)

  20. 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.

  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. 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.

  4. 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.

  5. Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx

    NARCIS (Netherlands)

    Deka, U.|info:eu-repo/dai/nl/325811202; Lezcano-Gonzalez, I.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Beale, A.M.|info:eu-repo/dai/nl/325802068

    2013-01-01

    Cu-exchanged zeolites have demonstrated widespread use as catalyst materials in the abatement of NOx, especially from mobile sources. Recent studies focusing on Cu-exchanged zeolites with the CHA structure have demonstrated them to be excellent catalysts in the ammonia-assisted selective catalytic

  6. Catalytic properties of niobium compounds

    International Nuclear Information System (INIS)

    Tanabe, K.; Iizuka, T.

    1983-04-01

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

  7. 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)

  8. 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.

  9. 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.

  10. Atmospheric oxidation of selected alcohols and esters

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K H; Cavalli, F

    2001-03-01

    The decision whether it is appropriate and beneficial for the environment to deploy specific oxygenated organic compounds as replacements for traditional solvent types requires a quantitative assessment of their potential atmospheric impacts including tropospheric ozone and other photooxidant formation. This involves developing chemical mechanisms for the gasphase atmospheric oxidation of the compounds which can be reliably used in models to predict their atmospheric reactivity under a variety of environmental conditions. Until this study, there was very little information available concerning the atmospheric fate of alcohols and esters. The objectives of this study were to measure the atmospheric reaction rates and to define atmospheric reaction mechanisms for the following selected oxygenated volatile organic compounds: the alcohols, 1-butanol and 1-pentanol, and the esters, methyl propionate and dimethyl succinate. The study has successfully addressed these objectives. (orig.)

  11. 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.

  12. 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

  13. 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...

  14. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    Science.gov (United States)

    Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  15. Nitroxide-catalyzed selective oxidation of alcohols and polysaccharides

    International Nuclear Information System (INIS)

    Ponedel'kina, I Yu; Khaibrakhmanova, E A; Odinokov, Viktor N

    2010-01-01

    The use of nitroxide radicals in the selective oxidation of alcohols is considered. Attention is focused on the oxidation of polysaccharides as a method of preparation of polyuronic acids, aldehydes and hemiacetals.

  16. Process for selected gas oxide removal by radiofrequency catalysts

    Science.gov (United States)

    Cha, Chang Y.

    1993-01-01

    This process to remove gas oxides from flue gas utilizes adsorption on a char bed subsequently followed by radiofrequency catalysis enhancing such removal through selected reactions. Common gas oxides include SO.sub.2 and NO.sub.x.

  17. Effects of γ- and x-irradiation upon activity and selectivity of a supported silver catalyst in the oxidation of ethylene and carbon monoxide

    International Nuclear Information System (INIS)

    Mora Vallejo, R.J.

    1975-01-01

    Effects of γ and x-radiation on catalytic selectivity of supported silver catalysts for production of ethylene oxide via ethylene oxidation were compared by determination of radio-induced changes in conversion-yield profiles. Influence of photon energy on the kinetics of the irradiation process was studied by determination of conversion-yield profiles, using samples of catalyst exposed to x-rays of different mean photon energy and γ-rays for different cumulative periods of time. The effect of γ-radiation on catalytic activity of the same silver catalysts for carbon monoxide oxidation was analyzed by determination of the reaction kinetics before and after catalyst irradiation

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. Development of a coupled reactor with a catalytic combustor and steam reformer for a 5 kW solid oxide fuel cell system

    International Nuclear Information System (INIS)

    Kang, Sanggyu; Lee, Kanghun; Yu, Sangseok; Lee, Sang Min; Ahn, Kook-Young

    2014-01-01

    Highlights: • Proposes the scale-up strategy to develop a large-scale coupled reactor. • Investigation of performance of steam reformer coupled with catalytic combustor. • Experimental parameters are inlet temp., air excess ratio, SCR, fuel utilization. • Evaluation of the heat transfer distribution along the gas flow direction. • The mean value of methane conversion rate is approximately 93.4%. - Abstract: The methane (CH 4 ) conversion rate of a steam reformer can be increased by thermal integration with a catalytic combustor, called a coupled reactor. In the present study, a 5 kW coupled reactor has been developed based on a 1 kW coupled reactor in previous work. The geometric parameters of the space velocity, diameter and length of the coupled reactor selected from the 1 kW coupled reactor are tuned and applied to the design of the 5 kW coupled reactor. To confirm the scale-up strategy, the performance of 5 kW coupled reactor is experimentally investigated with variations of operating parameters such as the fuel utilization in the solid oxide fuel cell (SOFC) stack, the inlet temperature of the catalytic combustor, the excess air ratio of the catalytic combustor, and the steam to carbon ratio (SCR) in the steam reformer. The temperature distributions of coupled reactors are measured along the gas flow direction. The gas composition at the steam reformer outlet is measured to find the CH 4 conversion rate of the coupled reactor. The maximum value of the CH 4 conversion rate is approximately 93.4%, which means the proposed scale-up strategy can be utilized to develop a large-scale coupled reactor

  4. Selective nano alumina supported vanadium oxide catalysts for oxidative dehydrogenation of ethylbenzene to styrene using CO2 as soft oxidant

    Directory of Open Access Journals (Sweden)

    A.M. Elfadly

    2013-12-01

    Full Text Available Nano alumina-supported V2O5 catalysts with different loadings have been tested for the dehydrogenation of ethylbenzene with CO2 as an oxidant. High surface area nano-alumina was prepared and used as support for V2O5 as the catalyst. The catalysts were synthesized by impregnation techniques followed by calcinations and microwave treatment, denoted as V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW, respectively. The V2O5 loading was varied on nano-alumina from 5 to 30 wt%. The support and catalysts were characterized by X-ray diffraction (XRD, Barett–Joyner–Halenda (BJH pore-size distribution, N2-adsorption isotherms, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and temperature programed desorption (TPD-NH3. The characterization results indicated that V2O5 is highly dispersed on alumina up to 30%-V2O5/γ-Al2O3-MW prepared by MW method. The TPD studies indicated that there are significant differences in acid amount and strength for V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW-catalysts. The catalytic activity of the prepared catalysts was evaluated in the temperature range 450–600 °C in relation to the physicochemical properties and surface acidity. The results revealed that optimum catalytic activity and selectivity (∼100% toward styrene production were obtained using 10% V2O5/γ-Al2O3-MW catalyst treated with microwave.

  5. 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.

  6. Outline of laundry drainage treatment system combining catalytic oxidation and filtration

    International Nuclear Information System (INIS)

    Kanda, Masanori; Matsuzaki, Susumu; Kikkawa, Ryouzo; Masuda, Kazumichi; Takeuchi, Kimihito; Urabe, Osamu

    2011-01-01

    We plan to use a laundry drainage treatment system that combines a device using a manganese dioxide-based catalyst for ozone oxidation with a ceramic microfiltration membrane (MF membrane). The high oxidizing power of ozone is enhanced by the catalyst, and the impurities (such as chemical oxygen demand (COD) causative substances and n-hexane extracts) in the drainage are sufficiently degraded to allow their releases to the environment. Ionic nuclides are also oxidized and in solubilized so that they can be separated with the MF membrane having fine pores of about 0.1 μm. The performance of the treatment system in removing radioactivity, COD causative substances, and n-hexane extracts was confirmed by hot demonstration tests using actual laundry drainage. Cold tests were also conducted using simulated laundry drainage to confirm the system operation conditions and the long-term stability of drainage treatment capability. While ozone has a high oxidizing power, it decays spontaneously in liquid within a short period of time. Therefore, the behavior of ozone under the operating conditions and its effect on the corrosion of structural materials were investigated to maintain a sufficient time for decay and select appropriate structural materials. (author)

  7. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NO{sub x} with NH{sub 3} at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Peng [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Sun, Hong [School of Environmental & Chemical Engineering, Dalian Jiaotong University, Dalian 116028 (China); Quan, Xie, E-mail: quanxie@dlut.edu.cn [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China); Chen, Shuo [School of Environmental Science and Technology, Dalian University of Technology, Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), Dalian 116024 (China)

    2016-01-15

    Highlights: • Nano-ceria was successfully encapsulated into MIL-100(Fe) for the SCR of NO{sub x}. • The incorporated ceria in MIL-100(Fe) showed high content of chemisorbed oxygen. • The added ceria into MIL-100(Fe) improved the formation of adsorbed NO{sub 2} species. • The addition of ceria into MIL-100(Fe) enhanced SCR activity at low temperature. - Abstract: The development of catalysts for selective catalytic reduction (SCR) reactions that are highly active at low temperatures and show good resistance to SO{sub 2} and H{sub 2}O is still a challenge. In this study, we have designed and developed a high-performance SCR catalyst based on nano-sized ceria encapsulated inside the pores of MIL-100(Fe) that combines excellent catalytic power with a metal organic framework architecture synthesized by the impregnation method (IM). Transmission electron microscopy (TEM) revealed the encapsulation of ceria in the cavities of MIL-100(Fe). The prepared IM-CeO{sub 2}/MIL-100(Fe) catalyst shows improved catalytic activity both at low temperatures and throughout a wide temperature window. The temperature window for 90% NO{sub x} conversion ranges from 196 to 300 °C. X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analysis indicated that the nano-sized ceria encapsulated inside MIL-100(Fe) promotes the production of chemisorbed oxygen on the catalyst surface, which greatly enhances the formation of the NO{sub 2} species responsible for fast SCR reactions.

  8. Ni/MgAlO regeneration for catalytic wet air oxidation of an azo-dye in trickle-bed reaction.

    Science.gov (United States)

    Vallet, Ana; Ovejero, Gabriel; Rodríguez, Araceli; Peres, José A; García, Juan

    2013-01-15

    Active nickel catalysts (7 wt%) supported over Mg-Al mixed oxides have been recently developed and it has also been demonstrated that they are also highly selective in Catalytic Wet air Oxidation (CWAO) of dyes. CWAO of Chromotrope 2R (C2R) has been studied using a trickle bed reactor employing temperatures from 100 to 180 °C, liquid flow rates from 0.1 to 0.7 mL min(-1) and initial dye concentration from 10 to 50 ppm. Total pressure and air flow were 25 bar and 300 mL min(-1), respectively. The catalyst showed a very stable activity up to 24 h on stream with an average TOC conversion of 82% at 150 °C and T(r)=0.098 g(Ni) min mL(-1). After the reaction, a 1.1 wt% C of carbonaceous deposit is formed onto the catalyst and a diminution of 30% of the surface area with respect of the fresh catalyst was observed. An increase in the space time gave higher TOC conversions up to T(r)=0.098 g(Ni) min mL(-1), attaining values of 80% at 180 °C. The performance of TOC and dye removal does not decrease after two regeneration cycles. In total, a 57 h effective reaction has been carried out with no loss of catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

    International Nuclear Information System (INIS)

    Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin

    2015-01-01

    Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

  10. 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

  11. 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.

  12. Research and proposal on selective catalytic reduction reactor optimization for industrial boiler.

    Science.gov (United States)

    Yang, Yiming; Li, Jian; He, Hong

    2017-08-24

    The advanced computational fluid dynamics (CFD) software STAR-CCM+ was used to simulate a denitrification (De-NOx) project for a boiler in this paper, and the simulation result was verified based on a physical model. Two selective catalytic reduction (SCR) reactors were developed: reactor 1 was optimized and reactor 2 was developed based on reactor 1. Various indicators, including gas flow field, ammonia concentration distribution, temperature distribution, gas incident angle, and system pressure drop were analyzed. The analysis indicated that reactor 2 was of outstanding performance and could simplify developing greatly. Ammonia injection grid (AIG), the core component of the reactor, was studied; three AIGs were developed and their performances were compared and analyzed. The result indicated that AIG 3 was of the best performance. The technical indicators were proposed for SCR reactor based on the study. Flow filed distribution, gas incident angle, and temperature distribution are subjected to SCR reactor shape to a great extent, and reactor 2 proposed in this paper was of outstanding performance; ammonia concentration distribution is subjected to ammonia injection grid (AIG) shape, and AIG 3 could meet the technical indicator of ammonia concentration without mounting ammonia mixer. The developments above on the reactor and the AIG are both of great application value and social efficiency.

  13. A fuzzy logic urea dosage controller design for two-cell selective catalytic reduction systems.

    Science.gov (United States)

    You, Kun; Wei, Lijiang; Jiang, Kai

    2017-12-22

    Diesel engines have dominated in the heavy-duty vehicular and marine power source. However, the induced air pollution is a big problem. As people's awareness of environmental protection increasing, the emission regulations of diesel-engine are becoming more stringent. In order to achieve the emission regulations, the after-treatment system is a necessary choice. Specifically, the selective catalytic reduction (SCR) system has been widely applied to reduce the NO X emissions of diesel engine. Different from single-cell SCR systems, the two-cell systems have various benefits from the modeling and control perspective. In this paper, the urea dosage controller design for two-cell SCR systems was investigated. Firstly, the two-cell SCR modeling was introduced. Based on the developed model, the design procedure for the fuzzy logic urea dosage controller was well addressed. Secondly, simulations and comparisons were employed via an experimental verification of the whole vehicle simulator. And the results showed that the designed controller simultaneously achieved high NO X reduction rate and low tail-pipe ammonia slip. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  14. Nanocarbons as catalyst for selective oxidation of acrolein to acrylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Frank, B.; Blume, R.; Rinaldi, A.; Trunschke, A.; Schloegl, R. [Fritz Haber Institute of the Max Planck Society, Berlin (Germany). Dept. of Inorganic Chemistry

    2011-07-01

    Selective oxidations are key steps of industrial oil and gas processing for the synthesis of high-value chemicals. Mixed metal oxides based on redox active V or Mo are frequently used for oxidative C-H bond activation. However, multiple processes require precious metals or suffer from low product selectivity demanding an ongoing search for cost-effective alternatives. Recently, the nanostructured carbon was reported to catalyze the metal-free selective alkane activation by oxidative dehydrogenation (ODH). Electron-rich surface carbonyls coordinate this reaction and mimic the active oxygen species in metal oxide catalysts. Here we show that the graphitic carbon, beyond ODH, has the potential to selectively mediate the insertion of an oxygen atom into an organic molecule, i.e., acrolein. Multi-step atom rearrangements considerably exceed the mechanistic complexity of hydrogen abstraction and were so far believed to be the exclusive domain of metal (oxide) catalysis. In the carbon catalyzed process, the nucleophilic oxygen atoms terminating the graphite (0001) surface abstract the formyl hydrogen and the activated aldehyde gets oxidized by epoxide-type mobile oxygen, thus the sp{sup 2} carbon acts as a bifunctional catalyst. Substantial similarities between the metal oxide- and carbon-catalyzed reactions could be identified. Our results shed light on a rarely known facet of applications of nanostructured carbon materials being decorated with diverse oxygen functionalities to coordinate complex catalytic processes. We could successfully transfer the results obtained from the graphite model to carbon nanotubes (CNTs) providing a higher surface area, defect density, and intrinsic activity, to substantially increase the reactivity per catalyst volume. Indeed, low dimensional nanostructured carbon is a highly flexible and robust material which can be modified in a multiple manner to optimize its properties with respect to the intended application. The exploration of

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. Design of Highly Selective Gas Sensors via Physicochemical Modification of Oxide Nanowires: Overview

    Directory of Open Access Journals (Sweden)

    Hyung-Sik Woo

    2016-09-01

    Full Text Available Strategies for the enhancement of gas sensing properties, and specifically the improvement of gas selectivity of metal oxide semiconductor nanowire (NW networks grown by chemical vapor deposition and thermal evaporation, are reviewed. Highly crystalline NWs grown by vapor-phase routes have various advantages, and thus have been applied in the field of gas sensors over the years. In particular, n-type NWs such as SnO2, ZnO, and In2O3 are widely studied because of their simple synthetic preparation and high gas response. However, due to their usually high responses to C2H5OH and NO2, the selective detection of other harmful and toxic gases using oxide NWs remains a challenging issue. Various strategies—such as doping/loading of noble metals, decorating/doping of catalytic metal oxides, and the formation of core–shell structures—have been explored to enhance gas selectivity and sensitivity, and are discussed herein. Additional methods such as the transformation of n-type into p-type NWs and the formation of catalyst-doped hierarchical structures by branch growth have also proven to be promising for the enhancement of gas selectivity. Accordingly, the physicochemical modification of oxide NWs via various methods provides new strategies to achieve the selective detection of a specific gas, and after further investigations, this approach could pave a new way in the field of NW-based semiconductor-type gas sensors.

  20. Characterization of Catalytic Fast Pyrolysis Oils: The Importance of Solvent Selection for Analytical Method Development

    Energy Technology Data Exchange (ETDEWEB)

    Ferrell, Jack R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ware, Anne E [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-02-25

    Two catalytic fast pyrolysis (CFP) oils (bottom/heavy fraction) were analyzed in various solvents that are used in common analytical methods (nuclear magnetic resonance - NMR, gas chromatography - GC, gel permeation chromatography - GPC, thermogravimetric analysis - TGA) for oil characterization and speciation. A more accurate analysis of the CFP oils can be obtained by identification and exploitation of solvent miscibility characteristics. Acetone and tetrahydrofuran can be used to completely solubilize CFP oils for analysis by GC and tetrahydrofuran can be used for traditional organic GPC analysis of the oils. DMSO-d6 can be used to solubilize CFP oils for analysis by 13C NMR. The fractionation of oils into solvents that did not completely solubilize the whole oils showed that miscibility can be related to the oil properties. This allows for solvent selection based on physico-chemical properties of the oils. However, based on semi-quantitative comparisons of the GC chromatograms, the organic solvent fractionation schemes did not speciate the oils based on specific analyte type. On the other hand, chlorinated solvents did fractionate the oils based on analyte size to a certain degree. Unfortunately, like raw pyrolysis oil, the matrix of the CFP oils is complicated and is not amenable to simple liquid-liquid extraction (LLE) or solvent fractionation to separate the oils based on the chemical and/or physical properties of individual components. For reliable analyses, for each analytical method used, it is critical that the bio-oil sample is both completely soluble and also not likely to react with the chosen solvent. The adoption of the standardized solvent selection protocols presented here will allow for greater reproducibility of analysis across different users and facilities.

  1. Selective oxidation of propylene to acrolein by hydrothermally synthesized bismuth molybdates

    DEFF Research Database (Denmark)

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

    2014-01-01

    Hydrothermal synthesis has been used as a soft chemical method to prepare bismuth molybdate catalysts for the selective oxidation of propylene to acrolein. All obtained samples displayed a plate-like morphology, but their individual aspect ratios varied with the hydrothermal synthesis conditions...... of nitric acid during hydrothermal synthesis enhanced both propylene conversion and acrolein yield, possibly due to a change in morphology. Formation of β-Bi2Mo2O9 was not observed under the applied conditions. In general, the catalytic performance of all samples decreased notably after calcination at 550...

  2. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

    KAUST Repository

    Wang, Liang

    2015-04-22

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen.

  3. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds

    Science.gov (United States)

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-04-01

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

  4. Multi-layered zinc oxide-graphene composite thin films for selective nitrogen dioxide sensing

    Science.gov (United States)

    Ghosh, A.; Bhowmick, T.; Majumder, S. B.

    2018-02-01

    In the present work, selective nitrogen dioxide (NO2) sensing characteristics of multi-layered graphene-zinc oxide (G-ZnO) thin films have been demonstrated at 150 °C. The response% of 5 ppm NO2 was measured to be 894% with response and recovery times estimated to be 150 s and 315 s, respectively. In these composite films, the interaction between graphene and zinc oxide is established through X-ray photoelectron spectroscopy in conjunction with the analyses of photoluminescence spectra. Superior NO2 sensing of these films is due to simultaneous chemiadsorption of molecular oxygen and NO2 gases onto graphene and ZnO surfaces, resulting in an appreciable increase in the depletion layer width and thereby the sensor resistance. The sensor responses for other reducing gases (viz., CO, H2, and i-C4H10) are postulated to be due to their catalytic oxidation on the sensor surface, resulting in a decrease in the sensor resistance upon gas exposure. At lower operating temperature, due to the molecular nature of the chemiadsorbed oxygen, poor catalytic oxidation leads to a far lower sensor response for reducing gases as compared to NO2. For mixed NO2 and reducing gas sensing, we have reported that fast Fourier transformation of the resistance transients of all these gases in conjunction with principal component analyses forms a reasonably distinct cluster and, therefore, could easily be differentiated.

  5. 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.

  6. 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.

  7. 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.

  8. Performance of a Novel Hydrophobic Mesoporous Material for High Temperature Catalytic Oxidation of Naphthalene

    Directory of Open Access Journals (Sweden)

    Guotao Zhao

    2014-01-01

    Full Text Available A high surface area, hydrophobic mesoporous material, MFS, has been successfully synthesized by a hydrothermal synthesis method using a perfluorinated surfactant, SURFLON S-386, as the single template. N2 adsorption and TEM were employed to characterize the pore structure and morphology of MFS. Static water adsorption test indicates that the hydrophobicity of MFS is significantly higher than that of MCM-41. XPS and Py-GC/MS analysis confirmed the existence of perfluoroalkyl groups in MFS which led to its high hydrophobicity. MFS was used as a support for CuO in experiments of catalytic combustion of naphthalene, where it showed a significant advantage over MCM-41 and ZSM-5. SEM was helpful in understanding why CuO-MFS performed so well in the catalytic combustion of naphthalene. Experimental results indicated that MFS was a suitable support for catalytic combustion of large molecular organic compounds, especially for some high temperature catalytic reactions when water vapor was present.

  9. Engineered catalytic biofilms for continuous large scale production of n-octanol and (S)-styrene oxide.

    Science.gov (United States)

    Gross, Rainer; Buehler, Katja; Schmid, Andreas

    2013-02-01

    This study evaluates the technical feasibility of biofilm-based biotransformations at an industrial scale by theoretically designing a process employing membrane fiber modules as being used in the chemical industry and compares the respective process parameters to classical stirred-tank studies. To our knowledge, catalytic biofilm processes for fine chemicals production have so far not been reported on a technical scale. As model reactions, we applied the previously studied asymmetric styrene epoxidation employing Pseudomonas sp. strain VLB120ΔC biofilms and the here-described selective alkane hydroxylation. Using the non-heme iron containing alkane hydroxylase system (AlkBGT) from P. putida Gpo1 in the recombinant P. putida PpS81 pBT10 biofilm, we were able to continuously produce 1-octanol from octane with a maximal productivity of 1.3 g L ⁻¹(aq) day⁻¹ in a single tube micro reactor. For a possible industrial application, a cylindrical membrane fiber module packed with 84,000 polypropylene fibers is proposed. Based on the here presented calculations, 59 membrane fiber modules (of 0.9 m diameter and 2 m length) would be feasible to realize a production process of 1,000 tons/year for styrene oxide. Moreover, the product yield on carbon can at least be doubled and over 400-fold less biomass waste would be generated compared to classical stirred-tank reactor processes. For the octanol process, instead, further intensification in biological activity and/or surface membrane enlargement is required to reach production scale. By taking into consideration challenges such as biomass growth control and maintaining a constant biological activity, this study shows that a biofilm process at an industrial scale for the production of fine chemicals is a sustainable alternative in terms of product yield and biomass waste production. Copyright © 2012 Wiley Periodicals, Inc.

  10. Metal-surfactant interaction as a tool to control the catalytic selectivity of Pd catalysts

    NARCIS (Netherlands)

    Perez-Coronado, A. M.; Calvo, L.; Baeza, J.A.; Palomar, J.; Lefferts, L.; Rodriguez, J-C.; Gilarranz, M.A.

    2017-01-01

    The catalytic activity of Palladium nanoparticles synthesized via sodium bis[2-ethylhexyl] sulfosuccinate (AOT)/isooctane reverse microemulsion was studied in nitrite reduction. The influence of reaction conditions and the synthesis and purification of the nanoparticles was evaluated. In the

  11. Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

    1980-02-21

    Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

  12. Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

    International Nuclear Information System (INIS)

    Oh, Kwang Seok; Woo, Seong Ihl

    2011-01-01

    A chemiluminescence-based analyzer of NO x gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NO x analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al 2 O 3 substrate was tested for the efficiency of NO x removal using a home-built 64-channel parallel and sequential tubular reactor. The NO x concentrations measured by the NO x analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al 2 O 3 . Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NO x analyzer allowed to select Pt-Ce (X) (X=1–3) and Pt–Fe (2) as the optimal catalysts for NO x removal: 73% NO x conversion was achieved with the Pt–Fe (2) alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO.

  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. 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 t