WorldWideScience

Sample records for promoted oxide catalysts

  1. Oxidation of 4-methoxy-1-naphthol on promoted platinum catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2017-07-01

    Full Text Available , July 2017, Volume 58, Issue 4, pp 441–447 Oxidation of 4-methoxy-1-naphthol on promoted platinum catalysts M. V. Maphoru J. Heveling S. Kesavan Pillai Abstract Oxidative coupling of naphthols is a useful method for the formation of new...

  2. Catalysts Promoted with Niobium Oxide for Air Pollution Abatement

    Directory of Open Access Journals (Sweden)

    Wendi Xiang

    2017-05-01

    Full Text Available Pt-containing catalysts are currently used commercially to catalyze the conversion of carbon monoxide (CO and hydrocarbon (HC pollutants from stationary chemical and petroleum plants. It is well known that Pt-containing catalysts are expensive and have limited availability. The goal of this research is to find alternative and less expensive catalysts to replace Pt for these applications. This study found that niobium oxide (Nb2O5, as a carrier or support for certain transition metal oxides, promotes oxidation activity while maintaining stability, making them candidates as alternatives to Pt. The present work reports that the orthorhombic structure of niobium oxide (formed at 800 °C in air promotes Co3O4 toward the oxidation of both CO and propane, which are common pollutants in volatile organic compound (VOC applications. This was a surprising result since this structure of Nb2O5 has a very low surface area (about 2 m2/g relative to the more traditional Al2O3 support, with a surface area of 150 m2/g. The results reported demonstrate that 1% Co3O4/Nb2O5 has comparable fresh and aged catalytic activity to 1% Pt/γ-Al2O3 and 1% Pt/Nb2O5. Furthermore, 6% Co3O4/Nb2O5 outperforms 1% Pt/Al2O3 in both catalytic activity and thermal stability. These results suggest a strong interaction between niobium oxide and the active component—cobalt oxide—likely by inducing an oxygen defect structure with oxygen vacancies leading to enhanced activity toward the oxidation of CO and propane.

  3. Oxidation catalyst

    Science.gov (United States)

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

    The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

  4. The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Li, X.; Seshan, Kulathuiyer; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

    1993-01-01

    The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production

  5. Oxidative coupling of methane over alkali-promoted simple molybdate catalysts

    International Nuclear Information System (INIS)

    Discoll, S.A.; Zhang, L.; Ozkan, U.S.

    1992-01-01

    The study of various metal oxides and alkali promoted metal oxide catalysts has received much interest in recent years after the earlier reports of ethylene synthesis through oxidative coupling of methane, and of achieving high selectivities over a Li/MgO catalyst under methane and oxygen cofeed conditions. The addition of promoter ions to several oxide catalysts has been studied to determine the effect of the promoter ion on catalytic activity and selectivity. The authors' work has focused on the use of alkali promoters for a simple molybdate catalyst. MnMoO 4 . A study of Na, Li, K, Mg, Ba, Mn, Co, Fe, Cu, Zn, and Ni molybdates by Kiwi et al showed that with the exception of NiMoO 4 , the molybdates were stable for long periods of time under reaction conditions for oxidative coupling. At a conversion level of about 60%, selectivities ranged from 9.8% to 16.6%. The MnMoO 4 and K 2 MnMoO 4 molybdates were the least selective catalysts. Another molybdate, PbMoO 4 , was studied by Baerns et al., with 19% selectivity to C 2 hydrocarbons at 1% conversion. An 11.4% conversion to form aldehyde was also reported. In this paper the authors report the characterization and catalytic behavior of MnMoO 4 catalysts promoted with either Li, Na, or K in oxidative coupling of methane

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-31

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

  7. Oxidative conversion of propane over lithium-promoted magnesia catalyst. I. Kinetics and mechanism

    NARCIS (Netherlands)

    Leveles, L.; Seshan, Kulathuiyer; Lercher, J.A.; Lefferts, Leonardus

    2003-01-01

    Oxidative conversion of lower alkanes over lithium-promoted magnesia catalysts offers a viable alternative for propene and ethene production. The catalytic performance of propane oxidative dehydrogenation and cracking shows yields up to 50% of olefin (propene and ethene). The reaction kinetics were

  8. Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment

    1975-11-01

    Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.

  9. Mechanistic insight into oxide-promoted palladium catalysts for the electro-oxidation of ethanol.

    Science.gov (United States)

    Martinez, Ulises; Serov, Alexey; Padilla, Monica; Atanassov, Plamen

    2014-08-01

    Recent advancements in the development of alternatives to proton exchange membrane fuel cells utilizing less-expensive catalysts and renewable liquid fuels, such as alcohols, has been observed for alkaline fuel cell systems. Alcohol fuels present the advantage of not facing the challenge of storage and transportation encountered with hydrogen fuel. Oxidation of alcohols has been improved by the promotion of alloyed or secondary phases. Nevertheless, currently, there is no experimental understanding of the difference between an intrinsic and a synergistic promotion effect in high-pH environments. This report shows evidence of different types of promotion effects on palladium electrocatalysts obtained from the presence of an oxide phase for the oxidation of ethanol. The correlation of mechanistic in situ IR spectroscopic studies with electrochemical voltammetry studies on two similar electrocatalytic systems allow the role of either an alloyed or a secondary phase on the mechanism of oxidation of ethanol to be elucidated. Evidence is presented for the difference between an intrinsic effect obtained from an alloyed system and a synergistic effect produced by the presence of an oxide phase. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ethanol electrooxidation on Pt/C and Pd/C catalysts promoted with oxide

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Changwei [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Shen, Pei kang [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Liu, Yingliang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China)

    2007-02-10

    This research aims to investigate Pd-based catalysts as a replacement for Pt-based catalysts for ethanol electrooxidation in alkaline media. The results show that Pd/C has a higher catalytic activity and better steady-state behaviour for ethanol oxidation than that of Pt/C. The effect of the addition of CeO{sub 2} and NiO to the Pt/C and Pd/C electrocatalysts on ethanol oxidation is also studied in alkaline media. The electrocatalysts with a weight ratio of noble metal (Pt, Pd) to CeO{sub 2} of 2:1 and a noble metal to NiO ration 6:1 show the highest catalytic activity for ethanol oxidation. The oxide promoted Pt/C and Pd/C electrocatalysts show a higher activity than the commercial E-TEK PtRu/C electrocatalyst for ethanol oxidation in alkaline media. (author)

  11. Influence of promoters and oxidants on propane dehydrogenation over chromium-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Shaporeva, N.Yu.; Trushin, D.V.; Gaidai, N.A.; Nekrasov, N.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2010-12-30

    Possibilities for increasing the efficiency of supported on SiO{sub 2} chromium-oxide catalysts in propane oxidative dehydrogenation in CO{sub 2} presence are investigated: the introduction of Li, Na, K, Ca in catalysts and the addition of O{sub 2} in the reaction mixture. It was been found that the positive role of K - the increase of the selectivity to propene and stability of catalysts at long-duration tests - appeared at the relation of Cr:K=20. It was shown that the presence of little amount of O{sub 2} (2%) in the reaction mixtures of propane and carbon dioxide resulted in the increase of propene yield and catalyst stability. (orig.)

  12. Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO

    Science.gov (United States)

    Liu, Changxiang; Gong, Lei; Dai, Runying; Lu, Meijuan; Sun, Tingting; Liu, Qian; Huang, Xigen; Huang, Zhong

    2017-09-01

    Mesoporous Mn-doped Co3O4 catalysts were successfully prepared via a dry soft reactive grinding method based on solid state reaction, and their catalytic performances on CO oxidation were evaluated at a high space velocity of 49,500 mL g-1 h-1. A significant promoted effect was observed once the atomic ratios of Mn/(Co+Mn) were lower than 10%, for instance, the temperature for 50% conversion decreased to about -60 °C, showing superior catalytic performance compared to the single metal oxide. Especially, the Mn-promoted Co3O4 catalyst with a Mn/(Co+Mn) molar ratio of 10% could convert 100% CO after 3000 min of time-on-steam without any deactivation at room temperature. As prepared catalysts were characterized by XRD, N2-adsorption/desorption, TEM, H2-TPR, O2-TPD and CO-titration analysis. The significant enhancement of performance for oxidation of CO over Mn-Co-O mixed oxides was associated with the high active oxygen species concentrations formed during the pretreatment in O2 atmosphere.

  13. Cobalt Fischer-Tropsch catalysts: influence of cobalt dispersion and titanium oxides promotion

    Energy Technology Data Exchange (ETDEWEB)

    Azib, H

    1996-04-10

    The aim of this work is to study the effect of Sol-Gel preparation parameters which occur in silica supported cobalt catalysts synthesis. These catalysts are particularly used for the waxes production in natural gas processing. The solids have been characterized by several techniques: transmission electron microscopy (TEM), X-ray absorption near edge spectroscopy (XANES), programmed temperature reduction (TPR), infrared spectroscopy (IR), ultraviolet spectroscopy (UV), Magnetism, thermodesorption of H{sub 2} (TPD). The results indicate that the control of the cobalt dispersion and oxide phases nature is possible by modifying Sol-Gel parameters. The catalytic tests in Fischer-Tropsch synthesis were conducted on a pilot unit under pressure (20 atm) and suggested that turnover rates were independent of Co crystallite size, Co phases in the solids (Co deg., cobalt silicate) and titanium oxide promotion. On the other methane, the C{sub 3}{sup +} hydrocarbon selectivity is increased with increasing crystallite size. Inversely, the methane production is favoured by very small crystallites, cobalt silicate increase and titanium addition. However, the latter, used as a cobalt promoter, has a benefic effect on the active phase stability during the synthesis. (author). 149 refs., 102 figs., 71 tabs.

  14. Electrochemical promotion of oxidative coupling of methane on platinum/polybenzimidazole catalyst

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Bjerrum, Niels

    2002-01-01

    The electrochemical promotion of catalytic methane oxidation was studied using a (CH4,O-2,Ar), Pt\\polybenzimidazole (PBI)-H3PO4\\Pt,(H-2,Ar) fuel cell at 135degreesC. It has been found that C2H2, CO2, and water are the main oxidation products. Without polarization the yield of C2H2 was 0......, meaning that there was a maximum promotion effect at a polarization of -0.15 V, or 0.45 V catalyst potential vs. a hydrogen electrode (3.8% C2H2 yield). The catalytic rate enhancement ratio, r(C-2)/r(o)(C-2), at this maximum was 4.2. There was no C2H2 production at polarization greater than or equal to0.......9% and the yield of CO2 was 7.3%. This means that C-2 open-circuit selectivity was approximately 11%. Open-circuit voltage was around 0.6 V. It has been shown that the CH4 --> C2H2 catalytic reaction can be electrochemically promoted at negative polarization and exhibits a clear "volcano-type'' promotion behavior...

  15. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

    2006-01-01

    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2 ...

  16. Studies on the promotion of nickel—alumina coprecipitated catalysts: III. Cerium oxide

    NARCIS (Netherlands)

    Lansink Rotgerink, H.G.J.; Slaa, J.C.; van Ommen, J.G.; Ross, J.R.H.

    1988-01-01

    Three series of cerium-promoted nickel—alumina catalysts with different nickel-to-aluminium ratios each containing different amounts of cerium have been prepared and characterized. The calcination and reduction behaviour were found not to be altered by the presence of cerium. Part of the promoter

  17. Studies on the promotion of nickel—alumina coprecipitated catalysts: I. Titanium oxide

    NARCIS (Netherlands)

    Lansink Rotgerink, H.G.J.; Mercera, P.D.L.; van Ommen, J.G.; Ross, J.R.H.

    1988-01-01

    A series of TiO2-promoted nickel—alumina catalysts has been prepared and characterized. The promoter was added in various proportions to a calcined coprecipitated nickel—alumina material by adsorption of the acetylacetonate complex of titanium, followed by further calcination and reduction. The

  18. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Wei Yuchen; Liu Chenwei; Chang Weijung; Wang Kuanwen

    2011-01-01

    Research highlights: → Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. → O 2 treatment results in obvious Ru segregation and formation of RuO 2 . → Catalysts treated in H 2 have the excellent CO de-poisoning ability. → N 2 treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O 2 treatment results in obvious Ru segregation and formation of RuO 2 . Catalysts treated in H 2 have the highest I f /I b value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N 2 treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion (∼60% Pt on the surface), make the components stable and hence promote the MOR significantly.

  19. Promotion of Pt-Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wei Yuchen; Liu Chenwei; Chang Weijung [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China); Wang Kuanwen, E-mail: kuanwen.wang@gmail.com [Institute of Materials Science and Engineering, National Central University, Taoyuan 32001, Taiwan (China)

    2011-01-12

    Research highlights: > Thermal treatments on the Pt-Ru/C induce different extents of surface segregation. > O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. > Catalysts treated in H{sub 2} have the excellent CO de-poisoning ability. > N{sub 2} treatment suppresses the surface Pt depletion and hence promotes the MOR. - Abstract: Carbon supported Pt-Ru/C (1:1) alloy catalysts supplied by E-TEK are widely used for fuel cell research. Heat treatments in various atmospheres are conducted for the promotion of the methanol oxidation reaction (MOR) and the investigation of the structure-activity relationship (SAR) of the catalysts. The alloy structures, surface compositions, surface species, and electro-catalytic activities of the alloy catalysts are characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV), respectively. The as-received Pt-Ru/C catalysts have a Ru rich in the inner core and Pt rich on the outer shell structure. Thermal treatments on the catalysts induce Ru surface segregation in different extents and thereby lead to their alteration of the alloying degrees. O{sub 2} treatment results in obvious Ru segregation and formation of RuO{sub 2}. Catalysts treated in H{sub 2} have the highest I{sub f}/I{sub b} value in the CV scans among all samples, indicating the catalysts have the excellent CO de-poisoning ability as evidenced by anodic CO stripping experiments. N{sub 2} treatment may serve as an adjustment process for the surface composition and structure of the catalysts, which can suppress the surface Pt depletion ({approx}60% Pt on the surface), make the components stable and hence promote the MOR significantly.

  20. Systematic Identification of Promoters for Methane Oxidation Catalysts Using Size- and Composition-Controlled Pd-Based Bimetallic Nanocrystals.

    Science.gov (United States)

    Willis, Joshua J; Goodman, Emmett D; Wu, Liheng; Riscoe, Andrew R; Martins, Pedro; Tassone, Christopher J; Cargnello, Matteo

    2017-08-30

    Promoters enhance the performance of catalytic active phases by increasing rates, stability, and/or selectivity. The process of identifying promoters is in most cases empirical and relies on testing a broad range of catalysts prepared with the random deposition of active and promoter phases, typically with no fine control over their localization. This issue is particularly relevant in supported bimetallic systems, where two metals are codeposited onto high-surface area materials. We here report the use of colloidal bimetallic nanocrystals to produce catalysts where the active and promoter phases are colocalized to a fine extent. This strategy enables a systematic approach to study the promotional effects of several transition metals on palladium catalysts for methane oxidation. In order to achieve these goals, we demonstrate a single synthetic protocol to obtain uniform palladium-based bimetallic nanocrystals (PdM, M = V, Mn, Fe, Co, Ni, Zn, Sn, and potentially extendable to other metal combinations) with a wide variety of compositions and sizes based on high-temperature thermal decomposition of readily available precursors. Once the nanocrystals are supported onto oxide materials, thermal treatments in air cause segregation of the base metal oxide phase in close proximity to the Pd phase. We demonstrate that some metals (Fe, Co, and Sn) inhibit the sintering of the active Pd metal phase, while others (Ni and Zn) increase its intrinsic activity compared to a monometallic Pd catalyst. This procedure can be generalized to systematically investigate the promotional effects of metal and metal oxide phases for a variety of active metal-promoter combinations and catalytic reactions.

  1. Studies on the promotion of nickel—alumina coprecipitated catalysts: II. Lanthanum oxide

    NARCIS (Netherlands)

    Lansink Rotgerink, H.G.J.; Paalman, R.P.A.M.; van Ommen, J.G.; Ross, J.R.H.

    1988-01-01

    Two series of lanthanum promoted nickel—alumina catalysts have been prepared by coprecipitation of the metal nitrates, using potassium carbonate. The molar ratio between nickel and the sum of aluminium and lanthanum was kept constant at 2.5 or 9.0 within each series. The calcination and reduction of

  2. Catalyst for Ammonia Oxidation

    DEFF Research Database (Denmark)

    2015-01-01

    The present invention relates to a bimetallic catalyst for ammonia oxidation, a method for producing a bimetallic catalyst for ammonia oxidation and a method for tuning the catalytic activity of a transition metal. By depositing an overlayer of less catalytic active metal onto a more catalytic...

  3. Reducible oxide based catalysts

    Science.gov (United States)

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  4. Effect of Promoters in Co-Mn-Al Mixed Oxide Catalyst on N2O Decomposition

    Czech Academy of Sciences Publication Activity Database

    Karásková, K.; Obalová, L.; Jirátová, Květa; Kovanda, F.

    2010-01-01

    Roč. 160, č. 2 (2010), s. 480-487 ISSN 1385-8947 R&D Projects: GA ČR GA106/09/1664 Institutional research plan: CEZ:AV0Z40720504 Keywords : nitrous oxide * catalytic decomposition * promoter effect Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 3.074, year: 2010

  5. Chloro-benquinone Modified on Graphene Oxide as Metal-free Catalyst: Strong Promotion of Hydroxyl Radical and Generation of Ultra-Small Graphene Oxide

    Science.gov (United States)

    Zhao, He; Wang, Juehua; Zhang, Di; Dai, Qin; Han, Qingzhen; Du, Penghui; Liu, Chenming; Xie, Yongbing; Zhang, Yi; Cao, Hongbin; Fan, Zhuangjun

    2017-03-01

    Carbon-based metal-free catalyst has attracted more and more attention. It is a big challenge to improve catalytic activity of metal-free catalyst for decomposition of H2O2 to produce hydroxyl radical (HO•). Here, we report chloro-benquinone (TCBQ) modified on graphene oxide (GO) as metal-free catalyst for strong promotion of HO•. By the incorporation of GO, the HO• production by H2O2 and TCBQ is significantly promoted. Based on density functional theory, TCBQ modified GO (GO-TCBQ) is more prone to be nucleophilic attacked by H2O2 to yield HO• via electron transfer acceleration. Furthermore, the generated HO• can cut GO nanosheets into uniform ultra-small graphene oxide (USGO) through the cleavage of epoxy and C-C bonds. Interestingly, the damaged GO and in situ formed GO fragments can further enhance decomposition of H2O2 to produce HO•. Different from other catalytic processes, the GO-TCBQ metal-free catalysis process can be enhanced by GO itself, producing more HO•, and uniform USGO also can be generated. Thus, the metal free catalysis will be considered a fabrication method for uniform USGO, and may be extended to other fields including detoxifying organic pollutants and the application as disinfectants.

  6. Selective liquid-phase oxidation of alcohols catalyzed by a silver-based catalyst promoted by the presence of ceria

    DEFF Research Database (Denmark)

    Beier, Matthias Josef; Hansen, Thomas Willum; Grunwaldt, Jan-Dierk

    2009-01-01

    simultaneously. When a high catalytic conversion (>30% over 2 h) was found the number of catalyst components was reduced in the following tests. Thereby, a collaborative effect between a physical mixture of ceria nanoparticles and silver-impregnated silica (10 wt.% Ag–SiO2) was found. The catalytic activity...... by in situ XAS experiments. Oxygen species incorporated in the silver lattice appear to be important for the catalytic oxidation of the alcohol for which a preliminary mechanism is presented. The application of the catalyst was extended to the oxidation of a wide range of primary and secondary alcohols....... Compared to palladium and gold catalysts, the new silver catalyst performed similarly or even superior in the presence of CeO2. In addition, the presence of ceria increased the catalytic activity of all investigated catalysts....

  7. Silver-promoted catalyst for removal of nitrogen oxides from emission of diesel engines

    Energy Technology Data Exchange (ETDEWEB)

    Masuda, K.; Tsujimura, K. [New ACE Institute Co., Ltd., Ibaraki (Japan); Shinoda, K.; Kato, T. [Mitsui Mining and Smelting Co., Ltd. Ageo, Saitama (Japan)

    1996-02-29

    Removal of NO{sub x} from diesel exhaust gas using C{sub 3}H{sub 6}, CH{sub 3}OH or (CH{sub 3}){sub 2}O as a reducing agent was investigated on Ag/Al{sub 2}O{sub 3}, Ag/ZSM-5 and Ag/mordenite catalysts over a wide range of temperatures. Among them, (CH{sub 3}){sub 2}O was found to be suitable for the elimination of NO{sub x} over Ag/mordenite catalyst at the relatively low temperature of 200C to 350C. CH{sub 3}OH was suitable over Ag/Al{sub 2}O{sub 3} catalyst from 350C to 450C while the Ag/mordenite catalyst using (CH{sub 3}){sub 2}O was superior to the Ag/Al{sub 2}O{sub 3} catalyst using CH{sub 3}OH with respect to the temperature range. The Ag/ZSM-5 catalyst had a poor elimination ability when compared with Ag/Al{sub 2}O{sub 3} and Ag/mordenite catalysts. The effects of Ag on mordenite and Al{sub 2}O{sub 3} were also investigated. It was found that Ag improved the removal of NO{sub x} in the higher range of temperatures with mordenite, while Ag improved the removal of NO{sub x} in the lower temperature range with Al{sub 2}O{sub 3}. It was concluded that Ag/mordenite catalyst using (CH{sub 3}){sub 2}O as a reducing agent has a good ability for NO{sub x} removal over a wide range of temperatures

  8. Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)

    2016-06-17

    Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH4 and increase the selectivity toward C5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

  9. Thief carbon catalyst for oxidation of mercury in effluent stream

    Science.gov (United States)

    Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

    2011-12-06

    A catalyst for the oxidation of heavy metal contaminants, especially mercury (Hg), in an effluent stream is presented. The catalyst facilitates removal of mercury through the oxidation of elemental Hg into mercury (II) moieties. The active component of the catalyst is partially combusted coal, or "Thief" carbon, which can be pre-treated with a halogen. An untreated Thief carbon catalyst can be self-promoting in the presence of an effluent gas streams entrained with a halogen.

  10. Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

    Science.gov (United States)

    Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.

  11. Catalyst for Decomposition of Nitrogen Oxides

    Science.gov (United States)

    Schryer, David R. (Inventor); Jordan, Jeffrey D. (Inventor); Akyurtlu, Ates (Inventor); Akyurtlu, Jale (Inventor)

    2015-01-01

    This invention relates generally to a platinized tin oxide-based catalyst. It relates particularly to an improved platinized tin oxide-based catalyst able to decompose nitric oxide to nitrogen and oxygen without the necessity of a reducing gas.

  12. Perovskite catalysts for oxidative coupling

    Science.gov (United States)

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  13. Tin-antimony oxide oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

    1998-12-15

    Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

  14. Cerium promoted Fischer-Tropsch catalysts

    International Nuclear Information System (INIS)

    Fiato, R.A.; Bar-Gadda, R.; Miseo, S.

    1987-01-01

    This patent describes a hydrocarbon synthesis catalyst composition comprising sintered combination metal oxides having the following components in the stated weight percentage of the catalyst composition: (a) about 5 to about 80 weight percent Fe oxide; (b) about 4 to about 20 weight percent Zn oxide; (c) about 10 to about 40 weight percent Ti and/or Mn oxide; (d) about 1 to about 5 weight percent K, Rb, and/or Cs oxide; and (e) about 1 to about 10 weight percent Ce oxide, such that where the catalyst contains Fe, the sintered combination comprises a series of Fe, Zn, and/or Ti and/or Mn spinels and oxides of K, Rb and/or Cs, dispersed in a Ce oxide matrix

  15. TiO2 and Al2O3 promoted Pt/C nanocomposites as low temperature fuel cell catalysts for electro oxidation of methanol in acidic media

    International Nuclear Information System (INIS)

    Naeem, Rabia; Ahmed, Riaz; Ansari, Muhammad Shahid

    2014-01-01

    Carbon corrosion and platinum dissolution are the two major catalyst layer degradation problems in polymer electrolyte membrane fuel cells (PEMFC). Ceramic addition can reduce the corrosion of carbon and increase the stability of catalysts. Pt/TiO 2 , Pt/TiO 2 -C, Pt/Al 2 O 3 and Pt/Al 2 O 3 -C catalysts were synthesized and characterized. Electrochemical surface area of Pt/TiO 2 -C and Pt/Al 2 O 3 -C nanocomposite catalysts was much higher than the Pt/TiO 2 and Pt/Al 2 O 3 catalysts. Peak current, specific activity and mass activity of the catalysts was also determined by cyclic voltammetry and were much higher for the carbon nanocomposites. Exchange current densities were determined from Tafel plots. Heterogeneous rates of reaction of electro oxidation of methanol were determined for all the catalysts and were substantially higher for titania catalysts as compared to alumina added catalysts. Mass activity of Pt/TiO 2 -C was much higher than mass activity of Pt/Al 2 O 3 -C. Stability studies showed that addition of ceramics have increased the catalytic activity and durability of the catalysts considerably

  16. Nanoparticular metal oxide/anatase catalysts

    DEFF Research Database (Denmark)

    2010-01-01

    The present invention concerns a method of preparation of nanoparticular metal oxide catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular metal oxide catalyst precursors comprising combustible crystallization seeds upon which...... the catalyst metai oxide is co-precipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step. The present invention also concerns processes wherein the nanoparticular metal oxide catalysts of the invention are used, such as SCR (deNOx) reactions...

  17. Oxidation catalysts on alkaline earth supports

    Science.gov (United States)

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  18. Hydroprocessing with self-promoted molybdenum and tungsten sulfide catalyst

    International Nuclear Information System (INIS)

    Mc Candish, L.E.; Ho, T.C.

    1987-01-01

    A hydroprocessing process is described comprising contacting a hydrocarbon feed at elevated temperature of at least about 100 0 C and in the presence of hydrogen with a supported, self-promoted catalyst obtained by compositioning one or more catalyst precursors of the formula (ML) (Mo/sub y/W/sub 1-y/O/sub 4/) with an inorganic refractory oxide support and heating the composition in a non-oxidizing atmosphere in the presence of sulfur at elevated temperature for a time sufficient to form the catalyst. M comprises one or more divalent promoter metals, y is any value ranging from 0 to 1, and wherein L is one or more, neutral, nitrogen-containing ligands at least one of which is a chelating polydentate ligand. The contacting occurs for a time sufficient to convert at least a portion of the feed

  19. Catalyst for Carbon Monoxide Oxidation

    Science.gov (United States)

    Davis, Patricia; Brown, Kenneth; VanNorman, John; Brown, David; Upchurch, Billy; Schryer, David; Miller, Irvin

    2010-01-01

    In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the

  20. Oxidation catalysts and process for preparing same

    International Nuclear Information System (INIS)

    1980-01-01

    Compounds particularly suitable as oxidation catalysis are described, comprising specified amounts of uranium, antimony and tin as oxides. Processes for making and using the catalysts are described. (U.K.)

  1. Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

    International Nuclear Information System (INIS)

    Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

    1985-01-01

    Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

  2. Isotope exchange in oxide-containing catalyst

    Science.gov (United States)

    Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

    1989-01-01

    A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

  3. Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

    International Nuclear Information System (INIS)

    Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

    2013-01-01

    Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

  4. Heteropoly acid promoted catalyst for SCR of NOx with ammonia

    DEFF Research Database (Denmark)

    2012-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gases. In particular, the invention concerns a process, a highly alkali metal resistant heteropoly acid promoted catalyst and the use of said catalyst for removal of NOx from exhaust or flue gases, said gases...... comprising alkali or earth alkali metals. Such gases comprise for example flue gases arising from the burning of biomass, combined biomass and fossil fuel, and from waste incineration units. The process comprises the selective catalytic reduction (SCR) of NOx, such as nitrogen dioxide (NO2) and nitrogen...

  5. Heterogeneous Metal Catalysts for Oxidation Reactions

    Directory of Open Access Journals (Sweden)

    Md. Eaqub Ali

    2014-01-01

    Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

  6. Chemical engineering design of CO oxidation catalysts

    Science.gov (United States)

    Herz, Richard K.

    1987-01-01

    How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

  7. Nitrogen oxides storage catalysts containing cobalt

    Science.gov (United States)

    Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

    2010-10-12

    Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

  8. 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...

  9. Hydrous titanium oxide-supported catalysts

    International Nuclear Information System (INIS)

    Dosch, R.G.; Stohl, F.V.; Richardson, J.T.

    1990-01-01

    Catalysts were prepared on hydrous titanium oxide (HTO) supports by ion exchange of an active metal for Na + ions incorporated in the HTO support during preparation by reaction with the parent Ti alkoxide. Strong active metal-HTO interactions as a result of the ion exchange reaction can require significantly different conditions for activation as compared to catalysts prepared by more widely used incipient wetness methods. The latter catalysts typically involve conversion or while the HTO catalysts require the alteration of electrostatic bonds between the metal and support with subsequent alteration of the support itself. In this paper, the authors discuss the activation, via sulfidation or reduction, of catalysts consisting of Co, Mo, or Ni-Mo dispersed on HTO supports by ion exchange. Correlations between the activation process and the hydrogenation, hydrodeoxygenation, and hydrodesulfurization activities of the catalysts are presented

  10. 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

  11. Catalytic oxidation of volatile organic compounds (n-hexane, benzene, toluene, o-xylene promoted by cobalt catalysts supported on γ-Al2O3-CeO2

    Directory of Open Access Journals (Sweden)

    R. Balzer

    2014-09-01

    Full Text Available Cobalt catalysts supported on γ-alumina, ceria and γ-alumina-ceria, with 10 or 20%wt of cobalt load, prepared by the wet impregnation method and characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, field emission transmission electron microscopy (FETEM, N2 adsorption-desorption isotherms (BET/BJH methods, energy-dispersive X-ray spectroscopy (EDX, X-ray photoemission spectroscopy (XPS, O2-chemisorption and temperature programmed reduction (TPR were used to promote the oxidation of volatile organic compounds (n-hexane, benzene, toluene and o-xylene. For a range of low temperatures (50-350 °C, the activity of the catalysts with a higher cobalt load (20% wt was greater than that of the catalysts with a lower cobalt load (10% wt. The Co/γ-Al2O3-CeO2 catalytic systems presented the best performances. The results obtained in the characterization suggest that the higher catalytic activity of the Co20/γ-Al2O3-CeO2 catalyst may be attributed to the higher metal content and amount of oxygen vacancies, as well as the effects of the interaction between the cobalt and the alumina and cerium oxides.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  13. Novel metalloporphyrin catalysts for the oxidation of hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Showalter, M.C.; Nenoff, T.M.; Shelnutt, J.A.

    1996-11-01

    Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

  14. Selective Oxidations using Nanostructured Heterogeneous Catalysts

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen

    and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

  15. 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}.

  16. 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

  17. FY 2000 report on the promotion projects by Research Institute of Innovative Technology for the Earth. Proceedings of the international seminar (Reports presented to the international workshop for selective oxidation catalysts); 2000 nendo chikyu kankyo sangyo gijutsu kaihatsu suishin jigyo kokusai seminar jigyo shiryo. Sentaku sanka shokubai kokusai workshop hokokusho

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2001-03-01

    Described herein are the FY 2000 results of the international workshop for selective oxidation catalysts, promoted by RITE. The session of methane activation includes a comprehensive lecture on designs of selective alkane oxidation catalysts developed since the 1980s, describing the simplified catalyst design procedures and, at the same time, pointing out the vapor-phase reactions governing the overall reactions at high temperature. The session of alkane oxidation includes a lecture on oxidation of ethane into acrolein in the presence of a silica catalyst supporting isolated active sites, stressing necessity for controlling the vapor-phase reactions and importance of isolating the active sites. The session of crystalline materials includes a lecture on Ti-siting in Ti-containing molecular sieve and selective oxidation catalyst functions, concentrating discussion on oxidation with H{sub 2}O{sub 2} as the oxidant on TS-1. The session of engineering hybrid includes a lecture on catalytic partial oxidation of alkanes in millisecond reactors, describing that possibility of controlling the vapor-phase reactions in the presence of monolith, porous-plate catalysts in a reactor through which the reactant gases pass in a very short time, of the order of millisecond. (NEDO)

  18. An improved method of preparation of nanoparticular metal oxide catalysts

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step....

  19. Coke formation on hydrodesulphurization catalysts. [Including effects of different promoters

    Energy Technology Data Exchange (ETDEWEB)

    Ternan, M.; Furimsky, E.; Parsons, B.I.

    1979-02-01

    The extent of coke formation was measured on a number of different hydrodesulfurization catalysts, primarily as a function of the catalyst chemical composition. Variations in the concentration of MoO/sub 3/ on the alumina, the type of catalyst promoter, the promoter/MoO/sub 3/ ratio, the presulfiding material and the reaction temperature were made. Increases in the reaction rate caused by either changes in the catalyst composition or by moderate changes in the reaction temperature were compared to the catalyst coke content. It was suggested that two types of coke were present on the catalyst, a reactive coke which is subsequently converted to reaction products and an unreactive coke which blocks catalytic sites.

  20. 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.

  1. Catalysts for oxidation of mercury in flue gas

    Science.gov (United States)

    Granite, Evan J [Wexford, PA; Pennline, Henry W [Bethel Park, PA

    2010-08-17

    Two new classes of catalysts for the removal of heavy metal contaminants, especially mercury (Hg) from effluent gases. Both of these classes of catalysts are excellent absorbers of HCl and Cl.sub.2 present in effluent gases. This adsorption of oxidizing agents aids in the oxidation of heavy metal contaminants. The catalysts remove mercury by oxidizing the Hg into mercury (II) moieties. For one class of catalysts, the active component is selected from the group consisting of iridium (Ir) and iridum-platinum (Ir/Pt) alloys. The Ir and Ir/Pt alloy catalysts are especially corrosion resistant. For the other class of catalyst, the active component is partially combusted coal or "Thief" carbon impregnated with Cl.sub.2. Untreated Thief carbon catalyst can be self-activating in the presence of effluent gas streams. The Thief carbon catalyst is disposable by means of capture from the effluent gas stream in a particulate collection device (PCD).

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-31

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

  3. Catalyst for reduction of nitrogen oxides

    Science.gov (United States)

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  4. Chemical nature of catalysts of oxide nanoparticles in environment

    Indian Academy of Sciences (India)

    Carbon nanostructures (CNS) are often grown using oxide nanoparticles as catalyst in chemical vapour deposition and these oxides are not expected to survive as such during growth. In the present study, the catalysts of cobalt- and nickel oxide-based nanoparticles of sizes varying over a range have been reduced at 575 ...

  5. Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

    Science.gov (United States)

    Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

    2015-01-06

    The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

  6. Two Catalysts for Selective Oxidation of Contaminant Gases

    Science.gov (United States)

    Wright, John D.

    2011-01-01

    Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

  7. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis

    DEFF Research Database (Denmark)

    Kuld, Sebastian; Thorhauge, Max; Falsig, Hanne

    2016-01-01

    Promoter elements enhance the activity and selectivity of heterogeneous catalysts. Here, we show how methanol synthesis from synthesis gas over copper (Cu) nanoparticles is boosted by zinc oxide (ZnO) nanoparticles. By combining surface area titration, electron microscopy, activity measurement, d...

  8. Newly designed PdRuBi/N-Graphene catalysts with synergistic effects for enhanced ethylene glycol electro-oxidation

    International Nuclear Information System (INIS)

    Li, Tengfei; Huang, Yiyin; Ding, Kui; Wu, Peng; Abbas, Syed Comail; Ghausi, Muhammad Arsalan; Zhang, Teng; Wang, Yaobing

    2016-01-01

    Graphical abstract: We rationally design and synthesize a ternary PdRuBi/NG catalyst with significantly enhanced catalytic activity with synergetic effect of Ru and Bi towards ethylene glycol electro-oxidation. - Abstract: Palladium (Pd)-based catalysts are appealing electro-catalysts for alcohol oxidation reaction in fuel cell, but still not efficient as the complicated oxidation process and sluggish kinetic. Here we rationally design and synthesize a PdRuBi/NG tri-metallic catalyst with space synergetic effect for enhanced ethylene glycol electro-oxidation, in which both Ru and Bi in the catalyst are synergistic effective in promoting catalytic activity of Pd catalytic interlayer by electronic effect and surface modification mechanism respectively. It shows 4.2 times higher peak current density towards ethylene glycol electro-oxidation than commercial Pd/C catalyst, and the catalytic durability is also greatly improved.

  9. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

  10. Ce - promoted catalyst from hydrotalcites for CO2 reforming of methane: calcination temperature effect

    Directory of Open Access Journals (Sweden)

    Carlos Enrique Daza

    2012-01-01

    Full Text Available Ce-promoted Ni-catalysts from hydrotalcites were obtained. The effect of calcination temperature on the chemical and physical properties of the catalysts was studied. Several techniques were used to determine the chemical and physical characteristics of oxides. The apparent activation energies of reduction were determined. Catalytic experiments at 48 L g-1h-1 without pre-reduction in CO2 reforming of methane were performed. The spinel-like phase in these oxides was only formed at 1000 ºC. The reduction of Ni2+ in the oxides was clearly affected by the calcination temperature which was correlated with catalytic performance. The catalyst calcined at 700 ºC showed the greatest activity.

  11. Plasma and catalyst for the oxidation of NOx

    Science.gov (United States)

    Jõgi, Indrek; Erme, Kalev; Levoll, Erik; Raud, Jüri; Stamate, Eugen

    2018-03-01

    Efficient exhaust gas cleaning from NO x (NO and NO2) by absorption and adsorption based methods requires the oxidation of NO. The application of non-thermal plasma is considered as a promising oxidation method but the oxidation of NO by direct plasma remains limited due to the back-reaction of NO2 to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal-oxide catalysts in the improvement of oxidation efficiency for both direct and indirect plasma oxidation of NO x . The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst surfaces while the exact mechanism and extent of the effect were different for direct and indirect oxidation. In the case of direct plasma oxidation, both short and long lifetime oxygen species could reach the catalyst and participate in the oxidation of NO to NO2. The back-reaction in the plasma phase remained still important factor and limited the effect of catalyst. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst.

  12. Reactivation of a tin oxide-containing catalyst

    Science.gov (United States)

    Upchurch, Billy T. (Inventor); Miller, Irvin M. (Inventor); Brown, Kenneth G. (Inventor); Hess, Robert V. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Paulin, Patricia A. (Inventor)

    1989-01-01

    A method for the reactivation of a tin oxide-containing catalyst of a CO.sub.2 laser is provided. First, the catalyst is pretreated by a standard procedure. When the catalyst experiences diminished activity during usage, the heated zone surrounding the catalyst is raised to a temperature which is the operating temperature of the laser and 400.degree. C. for approximately one hour. The catalyst is exposed to the same laser gas mixture during this period. The temperature of the heated zone is then lowered to the operating temperature of the CO.sub.2 laser.

  13. Structure-activity relationships of carbon-supported platinum-bismuth and platinum-antimony oxidation catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2017-04-01

    Full Text Available Compositional and morphological studies on supported platinum are important for the improvement and expanded use of catalysts for oxidative coupling reactions. Nanocomposites consisting of 5% Pt supported on activated carbon and promoted with 5% Bi...

  14. Acid monolayer functionalized iron oxide nanoparticle catalysts

    Science.gov (United States)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  15. 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.

  16. Water oxidation catalysts and methods of use thereof

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

    2017-12-05

    Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

  17. Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

    Science.gov (United States)

    Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

    2015-03-06

    Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Mechanism-Based Design of Green Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rybak-Akimova, Elena [Tufts Univ., Medford, MA (United States)

    2015-03-16

    situation. Growing families of synthetic iron complexes that resemble active sites of metalloenzymes produce metal-based intermediates (rather than hydroxyl radicals) in reactions with oxygen donors. These complexes are very promising for selective oxygen and peroxide activation. In order to understand the mechanisms of metal-based small molecule activation, kinetically competent metal-oxygen intermediates must be identified. One of the grand challenges identified by the Department of Energy workshop "Catalysis for Energy" is understanding mechanisms and dynamics of catalyzed reactions. The research summarized herein focuses on detailed characterization of the formation and reactivity of various iron-peroxo- and iron-oxo intermediates that are involved in catalysis. Rates of rapid reactions were studied at low temperatures by a specialized technique termed cryogenic stopped-flow spectrophotometry. These measurements identified reaction conditions which favor the formation of catalytically competent oxidants. Chemical structures of reactive complexes was determined, and new, efficient catalysts for hydrocarbon oxidation were synthesized. Importantly, these catalysts are selective, they promote oxidation of hydrocarbons at a specific site. The catalysts are also efficient and robust, hundreds of cycles of substrate oxidation occur within minutes at room temperature. Furthermore, they enable utilization of environmentally friendly oxidants, such as hydrogen peroxide, which produces water as the only byproduct. Mechanistic insights uncovered the role of various acid-containing additives in catalytic oxidations. Proton delivery to the active catalytic sites facilitated oxidations, similarly to the catalytic pathways in metal-containing enzymes. Under certain conditions, two metals in one complex can act in concert, modeling the reactivity of a bacterial enzyme which converts methane into methanol. In related studies, a family of nickel complexes that react with carbon dioxide at

  19. Oxidation of 1-butene over uranium oxide (UO3)-antimony oxide (Sb2O3) catalysts

    NARCIS (Netherlands)

    Simons, T.; Houtman, P.N.; Schuit, G.C.A.

    1971-01-01

    The oxidative dehydrogenation of butene to butadiene over U-Sb catalysts was investigated. The presence of two compds., (UO2)Sb3O7 and Sb3U3O14, reported by Grasselli and Callahan (1969), was confirmed with (UO2)Sb3O7 being the actual catalyst. The reaction is first order in butene and zero order in

  20. Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

    2013-11-01

    Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

  1. Activity of platinum/carbon and palladium/carbon catalysts promoted by Ni2 P in direct ethanol fuel cells.

    Science.gov (United States)

    Li, Guoqiang; Feng, Ligang; Chang, Jinfa; Wickman, Björn; Grönbeck, Henrik; Liu, Changpeng; Xing, Wei

    2014-12-01

    Ethanol is an alternative fuel for direct alcohol fuel cells, in which the electrode materials are commonly based on Pt or Pd. Owing to the excellent promotion effect of Ni2 P that was found in methanol oxidation, we extended the catalyst system of Pt or Pd modified by Ni2 P in direct ethanol fuel cells. The Ni2 P-promoted catalysts were compared to commercial catalysts as well as to reference catalysts promoted with only Ni or only P. Among the studied catalysts, Pt/C and Pd/C modified by Ni2 P (30 wt %) showed both the highest activity and stability. Upon integration into the anode of a homemade direct ethanol fuel cell, the Pt-Ni2 P/C-30 % catalyst showed a maximum power density of 21 mW cm(-2) , which is approximately two times higher than that of a commercial Pt/C catalyst. The Pd-Ni2 P/C-30 % catalyst exhibited a maximum power density of 90 mW cm(-2) . This is approximately 1.5 times higher than that of a commercial Pd/C catalyst. The discharge stability on both two catalysts was also greatly improved over a 12 h discharge operation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  3. Plasma and catalyst for the oxidation of NOx

    DEFF Research Database (Denmark)

    Jõgi, Indrek; Erme, Kalev; Levoll, Erik

    2018-01-01

    . In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either...... by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst....... to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal...

  4. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    Directory of Open Access Journals (Sweden)

    Gary Jacobs

    2014-03-01

    Full Text Available This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts, ultra-small crystallites (e.g., <2–4.4 nm formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu, or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading. Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling.

  5. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    Science.gov (United States)

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

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

  6. Alkaline Ionic Liquid Modified Pd/C Catalyst as an Efficient Catalyst for Oxidation of 5-Hydroxymethylfurfural

    Directory of Open Access Journals (Sweden)

    Zou Bin

    2018-01-01

    Full Text Available Conversion of HMF into FDCA was carried out by a simple and green process based on alkaline ionic liquid (IL modified Pd/C catalyst (Pd/C-OH−. Alkaline ionic liquids were chosen to optimize Pd/C catalyst for special hydrophilicity and hydrophobicity, redox stability, and unique dissolving abilities for polar compounds. The Pd/C-OH− catalyst was successfully prepared and characterized by SEM, XRD, TG, FT-IR, and CO2-TPD technologies. Loading of alkaline ionic liquid on the surface of Pd/C was 2.54 mmol·g−1. The catalyst showed excellent catalytic activity in the HMF oxidation after optimization of reaction temperature, reaction time, catalyst amount, and solvent. Supported alkaline ionic liquid (IL could be a substitute and promotion for homogeneous base (NaOH. Under optimal reaction conditions, high HMF conversion of 100% and FDCA yield of 82.39% were achieved over Pd/C-OH− catalyst in water at 373 K for 24 h.

  7. The kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane over Li/Na/MgO catalysts

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Toebes, A.; Toebes, A.; van Ommen, J.G.; Seshan, Kulathuiyer; Ross, J.R.H.; Ross, J.R.H.

    1992-01-01

    Kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane catalysed by Li/MgO and Li/Na/MgO have been investigated. Initial rate measurements at 600°C; revealed that the Li/MgO catalyst produced C2H4, CO2, CO and H2 by parallel reactions whereas the sodium-promoted catalyst produced

  8. Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

    Science.gov (United States)

    Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

  9. Sulfidation of carbon-supported iron oxide catalysts

    NARCIS (Netherlands)

    Ramselaar, W.L.T.M.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Oers, van E.M.; Kraan, van der A.M.

    1989-01-01

    The sulfidation of carbon-supported iron oxide catalysts was studied by means of in-situ Mössbauer spectroscopy at temperatures down to 4.2 K. The catalysts were dried in two different ways and then sulfided in a flow of 10% H2S in H2 at temperatures between 293 and 773 K. Thiophene

  10. Simulation of N(2)O Abatement in Waste Gases by Its Decomposition over a K-Promoted Co-Mn-Al Mixed Oxide Catalyst

    Czech Academy of Sciences Publication Activity Database

    Obalová, L.; Jirátová, Květa; Karásková, K.; Kovanda, F.

    2011-01-01

    Roč. 32, 5/SI/ (2011), s. 816-820 ISSN 0253-9837. [6th International Conference on Environmental Catalysis (6th ICEC). Beijing, 12.09.2010-15.09.2010] Institutional research plan: CEZ:AV0Z40720504 Keywords : nitrous oxide * catalytic decomposition * nitric acid production Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.171, year: 2011

  11. Ordered meso- and macroporous perovskite oxide catalysts for emerging applications

    DEFF Research Database (Denmark)

    Arandiyan, Hamidreza; Wang, Yuan; Sun, Hongyu

    2018-01-01

    This feature article summarizes the recent progress in porous perovskite oxides as advanced catalysts for both energy conversion applications and various heterogeneous reactions. Recently, research has been focused on specifically designing porous perovskite materials so that large surface areas ...

  12. New efficient catalyst for ammonia synthesis: barium-promoted cobalt on carbon

    DEFF Research Database (Denmark)

    Hagen, Stefan; Barfod, Rasmus; Fehrmann, Rasmus

    2002-01-01

    Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia......Barium-promoted cobalt catalysts supported on carbon exhibit higher ammonia activities at synthesis temperatures than the commercial, multipromoted iron catalyst and also a lower ammonia...

  13. Aerobic Oxidation of Alcohols over Gold Catalysts: Role of Acid and Base

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; DeLa Riva, Andrew T.; Helveg, Stig

    2008-01-01

    Gold nanoparticles are deposited on potassium titanate nanowires and used as heterogeneous catalysts in the aerobic oxidation of benzyl alcohol in methanol to methyl benzoate at ambient conditions. The presence of a catalytic amount of base promotes the reaction and the formation of free benzoic...

  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. Oxidative coupling of 1-naphthols over noble and base metal catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2014-01-01

    Full Text Available Bismuth-promoted platinum catalysts were tested for the oxidative coupling of 2- and 4-substituted 1-naphthols at different temperatures and ambient pressure. The principal final products are the 3,3'-substituted 1,1'-binaphthalenylidene-4,4'-diones...

  16. Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

    Science.gov (United States)

    Ahmed, Maaz S.

    alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

  17. Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

    Science.gov (United States)

    Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

    2017-05-24

    Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

  18. Supramolecular water oxidation with Ru-bda-based catalysts.

    Science.gov (United States)

    Richmond, Craig J; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni

    2014-12-22

    Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1) , respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.

    2014-11-05

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.

  20. Plasma and catalyst for the oxidation of NOx

    DEFF Research Database (Denmark)

    Jögi, I.; Erme, K.; Levoll, E.

    2017-01-01

    The removal of NOx from the exhaust gases requires the oxidation of most abundant NO to NO2 or N2O5. The oxidation can be done by non-thermal plasma but the efficiency is limited due to the back-reaction of NO2 to NO by O radicals. Present contribution investigates the role of catalysts in the im......The removal of NOx from the exhaust gases requires the oxidation of most abundant NO to NO2 or N2O5. The oxidation can be done by non-thermal plasma but the efficiency is limited due to the back-reaction of NO2 to NO by O radicals. Present contribution investigates the role of catalysts...... in the improvement of oxidation efficiency based on the stationary and time-dependent studies of the NOx oxidation at different reactor configurations and experimental conditions. The plasma produced active oxygen species (O, O3) were shown to play an important role in the reactions taking place on the catalyst...... surfaces while the exact mechanism and extent of the effect depended on the reactor configuration. The effect of catalyst at different experimental conditions was quantitatively described with the aid of analytical lumped kinetic models derived for the NOx oxidation when the catalyst was directly...

  1. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  2. The acidic properties of mixed tin and antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Irving, E.A.; Taylor, D.

    1978-01-01

    The acidic properties of mixed tin + antimony oxide catalysts were studied in the isomerization of 3,3-dimethyl-1-butene, cyclopropane, 1-butene, and cis-2-butene and the dehydration of isopropanol over the mixed oxides outgassed at room temperature and 698/sup 0/K. Only the zero-order portions of the reaction were used for calculations. With catalysts outgassed at room temperature, weakly acidic sites were present, and all the reactions probably occurred by a carbonium ion mechanism with Broensted acid sites as a source of protons. The rates increased with increasing antimony content to a maximum at approx. 50 at. % and then decreased with further increase in the antimony content. Outgassing of the catalysts at 698/sup 0/K increased the isomerization rate of 3,3-dimethyl-1-butene, but decreased those for cyclopropane and isopropanol due to poisoning by the propylene produced. For 1-butene and cis-2-butene and catalysts outgassed at 698/sup 0/K, only catalysts with less than 50Vertical Bar3< antimony were active. The catalysts were poisoned by treatment with bases or with sodium acetate. A proposed correlation between rates and acidity led to the conclusion that the catalyst composition corresponding to maximum acidity differs from that for maximum selective oxidation activity. Graphs and 10 references.

  3. Electron microscopic studies of natural gas oxidation catalyst – Effects of thermally accelerated aging on catalyst microstructure

    DEFF Research Database (Denmark)

    Honkanen, Mari; Hansen, Thomas Willum; Jiang, Hua

    2017-01-01

    Structural changes of PtPd nanoparticles in a natural gas oxidation catalyst were studied at elevated temperatures in air and low-oxygen conditions and in situ using environmental transmission electron microscopy (ETEM). The fresh catalyst shows

  4. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  5. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-10-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

  6. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

  7. Cobalt oxide-molybdenum oxide-aluminum oxide catalyst : II. The structure of the catalyst

    NARCIS (Netherlands)

    Lipsch, J.M.J.G.; Schuit, G.C.A.

    1969-01-01

    The structure of the \\"Co molybdate on alumina\\" catalyst was investigated. Infrared spectra show that the Mo is present as MoO3. Reflection spectra lead to the conclusion that the Co is distributed throughout the bulk of the alumina as CoAl2O4, whereas the MoO3 is spread over the carrier surface,

  8. 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

  9. Soot oxidation over NOx storage catalysts. Activity and deactivation

    International Nuclear Information System (INIS)

    Krishna, K.; Makkee, M.

    2006-01-01

    Soot oxidation activity and deactivation of NO x storage and reduction (NSR) catalysts containing Pt, K, and Ba supported on Al 2 O 3 , are studied under a variety of reaction conditions. K-containing catalysts decrease soot oxidation temperature with O 2 alone and the presence of Pt further enhance the activity due to synergetic effect. The active species responsible for synergism on Pt/K-Al 2 O 3 are unstable and cannot be regenerated. Soot oxidation temperature decreases by about 150 o C with NO+O 2 exhaust feed gas and under lean conditions NSR system acts as catalysed soot filter (CSF). The reactions that are mainly responsible for decreasing soot oxidation temperature are: (1) soot oxidation with NO 2 followed by NO recycles to NO 2 , and (2) soot oxidation with O 2 assisted by NO 2 . Only a part of the stored NO x that is decomposed at high temperatures under lean conditions is found to be useful for soot oxidation. NO x storage capacity of NSR catalysts decreases upon ageing under soot oxidising conditions. This will lead to a decreased soot oxidation activity on stored nitrate decomposition. Pt/K-Al 2 O 3 catalyst is more active, but least stable compared with Pt/Ba-Al 2 O 3 . (author)

  10. 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.

  11. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS; A

    International Nuclear Information System (INIS)

    Carl R.F. Lund

    2001-01-01

    This report covers the second year of a project investigating water-gas shift catalysts for use in membrane reactors. It has been established that a simple iron high temperature shift catalyst becomes ineffective in a membrane reactor because the reaction rate is severely inhibited by the build-up of the product CO(sub 2). During the past year, an improved microkinetic model for water-gas shift over iron oxide was developed. Its principal advantage over prior models is that it displays the correct asymptotic behavior at all temperatures and pressures as the composition approaches equilibrium. This model has been used to explore whether it might be possible to improve the performance of iron high temperature shift catalysts under conditions of high CO(sub 2) partial pressure. The model predicts that weakening the surface oxygen bond strength by less than 5% should lead to higher catalytic activity as well as resistance to rate inhibition at higher CO(sub 2) partial pressures. Two promoted iron high temperature shift catalysts were studied. Ceria and copper were each studied as promoters since there were indications in the literature that they might weaken the surface oxygen bond strength. Ceria was found to be ineffective as a promoter, but preliminary results with copper promoted FeCr high temperature shift catalyst show it to be much more resistant to rate inhibition by high levels of CO(sub 2). Finally, the performance of sulfided CoMo/Al(sub 2)O(sub 3) catalysts under conditions of high CO(sub 2) partial pressure was simulated using an available microkinetic model for water-gas shift over this catalyst. The model suggests that this catalyst might be quite effective in a medium temperature water-gas shift membrane reactor, provided that the membrane was resistant to the H(sub 2)S that is required in the feed

  12. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    Formaldehyde (CH2O) may be synthesized industrially by selective oxidation of methanol over an iron-molybdate (Fe-Mo) oxide catalyst according to: CH3OH + ½O2 →CH2O + H2O. The reaction is normally carried out in a multitubular reactor with excess of air at 250-400 °C (yield = 90-95 %), known...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...

  13. OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

    Directory of Open Access Journals (Sweden)

    Y. J. O. Asencios

    Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

  14. Impacts of acid gases on mercury oxidation across SCR catalyst

    International Nuclear Information System (INIS)

    Zhuang, Ye; Laumb, Jason; Liggett, Richard; Holmes, Mike; Pavlish, John

    2007-01-01

    A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO 2 , and SO 3 on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O 2 , CO 2 , H 2 O, NO, NO 2 , and NH 3 , and N 2 . HCl, SO 2 , and SO 3 were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5-50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO 2 and SO 3 showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO 2 and SO 3 , by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO 2 (2000 ppm), and SO 3 (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst. (author)

  15. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

    1997-01-01

    Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

  16. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-08

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  17. Structural analysis of nickel doped cerium oxide catalysts for fuel reforming in solid oxide fuel cells

    Science.gov (United States)

    Cavendish, Rio

    As world energy demands increase, research into more efficient energy production methods has become imperative. Heterogeneous catalysis and nanoscience are used to promote chemical transformations important for energy production. These concepts are important in solid oxide fuel cells (SOFCs) which have attracted attention because of their potential to provide an efficient and environmentally favorable power generation system. The SOFC is also fuel-flexible with the ability to run directly on many fuels other than hydrogen. Internal fuel reforming directly in the anode of the SOFC would greatly reduce the cost and complexity of the device. Methane is the simplest hydrocarbon and a main component in natural gas, making it useful when testing catalysts on the laboratory scale. Nickel (Ni) and gadolinium (Gd) doped ceria (CeO 2) catalysts for potential use in the SOFC anode were synthesized with a spray drying method and tested for catalytic performance using partial oxidation of methane and steam reforming. The relationships between catalytic performance and structure were then investigated using X-ray diffraction, transmission electron microscopy, and environmental transmission electron microscopy. The possibility of solid solutions, segregated phases, and surface layers of Ni were explored. Results for a 10 at.% Ni in CeO2 catalyst reveal a poor catalytic behavior while a 20 at.% Ni in CeO2 catalyst is shown to have superior activity. The inclusion of both 10 at.% Gd and 10 at.% Ni in CeO2 enhances the catalytic performance. Analysis of the presence of Ni in all 3 samples reveals Ni heterogeneity and little evidence for extensive solid solution doping. Ni is found in small domains throughout CeO2 particles. In the 20 at.% Ni sample a segregated, catalytically active NiO phase is observed. Overall, it is found that significant interaction between Ni and CeO2 occurs that could affect the synthesis and functionality of the SOFC anode.

  18. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Khalid Khazzal Hummadi

    2009-06-01

    Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

  19. IR-doped ruthenium oxide catalyst for oxygen evolution

    Science.gov (United States)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  20. The oxidation of copper catalysts during ethylene epoxidation.

    Science.gov (United States)

    Greiner, M T; Jones, T E; Johnson, B E; Rocha, T C R; Wang, Z J; Armbrüster, M; Willinger, M; Knop-Gericke, A; Schlögl, R

    2015-10-14

    The oxidation of copper catalysts during ethylene epoxidation was characterized using in situ photoemission spectroscopy and electron microscopy. Gas chromatography, proton-transfer reaction mass spectrometry and electron-ionization mass spectrometry were used to characterize the catalytic properties of the oxidized copper. We find that copper corrodes during epoxidation in a 1 : 1 mixture of oxygen and ethylene. The catalyst corrosion passes through several stages, beginning with the formation of an O-terminated surface, followed by the formation of Cu2O scale and eventually a CuO scale. The oxidized catalyst exhibits measurable activity for ethylene epoxidation, but with a low selectivity of 8/2500) Cu2O forms and eventually covers the surface.

  1. A predictive tool for selective oxidation of hydrocarbons: optical basicity of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Moriceau, P.; Lebouteiller, A.; Bordes, E.; Courtine, P. [Universite de Technologie de Compiegne, 60 (France). Dept. de Genie Chimique

    1998-12-31

    Whatever the composition of the catalyst (promoted, supported, multicomponent, etc.) is, it is possible to calculate its electron donor capacity {Lambda}. However, one important question remains: How are the surface and the bulk values of {Lambda} related? Most oxidation catalysts exhibit either a layered structure as V{sub 2}O{sub 5}, and approximately {Lambda}{sub th}{proportional_to}{Lambda}{sub surf}, or a molecular structure as polyoxometallates, and no correction seems to be needed. Work is in progress on that point. Of great importance is also the actual oxidation and coordination states of cations at the stedy state: {Lambda}s have been calculated from the composition determined by XANES and XPS. Finally, the model is able to discriminate between `paraffins` and olefins as reactants. These calibration curves should help to find new catalysts. (orig.)

  2. 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.

  3. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  4. Templating Routes to Supported Oxide Catalysts by Design

    Energy Technology Data Exchange (ETDEWEB)

    Notestein, Justin M. [Northwestern Univ., Evanston, IL (United States)

    2016-09-08

    The rational design and understanding of supported oxide catalysts requires at least three advancements, in order of increasing complexity: the ability to quantify the number and nature of active sites in a catalytic material, the ability to place external controls on the number and structure of these active sites, and the ability to assemble these active sites so as to carry out more complex functions in tandem. As part of an individual investigator research program that is integrated with the Northwestern University Institute for Catalysis in Energy Processes (ICEP) as of 2015, significant advances were achieved in these three areas. First, phosphonic acids were utilized in the quantitative assessment of the number of active and geometrically-available sites in MOx-SiO2 catalysts, including nanocrystalline composites, co-condensed materials, and grafted structures, for M=Ti, Zr, Hf, Nb, and Ta. That work built off progress in understanding supported Fe, Cu, and Co oxide catalysts from chelating and/or multinuclear precursors to maximize surface reactivity. Secondly, significant progress was made in the new area of using thin oxide overcoats containing ‘nanocavities’ from organic templates as a method to control the dispersion and thermal stability of subsequently deposited metal nanoparticles or other catalytic domains. Similar methods were used to control surface reactivity in SiO2-Al2O3 acid catalysts and to control reactant selectivity in Al2O3-TiO2 photocatalysts. Finally, knowledge gained from the first two areas has been combined to synthesize a tandem catalyst for hydrotreating reactions and an orthogonal tandem catalyst system where two subsequent reactions in a reaction network are independently controlled by light and heat. Overall, work carried out under this project significantly advanced the knowledge of synthesis-structure-function relationships in supported

  5. Reactivation of a Tin-Oxide-Containing Catalyst

    Science.gov (United States)

    Hess, Robert; Sidney, Barry; Schryer, David; Miller, Irvin; Miller, George; Upchurch, Bill; Davis, Patricia; Brown, Kenneth

    2010-01-01

    The electrons in electric-discharge CO2 lasers cause dissociation of some CO2 into O2 and CO, and attach themselves to electronegative molecules such as O2, forming negative O2 ions, as well as larger negative ion clusters by collisions with CO or other molecules. The decrease in CO2 concentration due to dissociation into CO and O2 will reduce the average repetitively pulsed or continuous wave laser power, even if no disruptive negative ion instabilities occur. Accordingly, it is the primary object of this invention to extend the lifetime of a catalyst used to combine the CO and O2 products formed in a laser discharge. A promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide (Pt/SnO2). First, the catalyst is pretreated by a standard procedure. The pretreatment is considered complete when no measurable quantity of CO2 is given off by the catalyst. After this standard pretreatment, the catalyst is ready for its low-temperature use in the sealed, high-energy, pulsed CO2 laser. However, after about 3,000 minutes of operation, the activity of the catalyst begins to slowly diminish. When the catalyst experiences diminished activity during exposure to the circulating gas stream inside or external to the laser, the heated zone surrounding the catalyst is raised to a temperature between 100 and 400 C. A temperature of 225 C was experimentally found to provide an adequate temperature for reactivation. During this period, the catalyst is still exposed to the circulating gas inside or external to the laser. This constant heating and exposing the catalyst to the laser gas mixture is maintained for an hour. After heating and exposing for an appropriate amount of time, the heated zone around the catalyst is allowed to return to the nominal operating temperature of the CO2 laser. This temperature normally resides in the range of 23 to 100 C. Catalyst activity can be measured as the percentage conversion of CO to CO2. In the specific embodiment

  6. Perovskite Catalysts—A Special Issue on Versatile Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Yu-Chuan Lin

    2014-08-01

    Full Text Available Perovskite-type catalysts have been prominent oxide catalysts for many years due to attributes such as flexibility in choosing cations, significant thermal stability, and the unique nature of lattice oxygen. Nearly 90% metallic elements of the Periodic Table can be stabilized in perovskite’s crystalline framework [1]. Moreover, by following the Goldschmidt rule [2], the A- and/or B-site elements can be partially substituted, making perovskites extremely flexible in catalyst design. One successful example is the commercialization of noble metal-incorporated perovskites (e.g., LaFe0.57Co0.38Pd0.05O3 for automotive emission control used by Daihatsu Motor Co. Ltd. [3]. Thus, growing interest in, and application of perovskites in the fields of material sciences, heterogeneous catalysis, and energy storage have prompted this Special Issue on perovskite catalysts. [...

  7. Effect of catalysts on heterogeneous oxidation of coal

    Energy Technology Data Exchange (ETDEWEB)

    Glazkova, A P; Kazarova, Yu A; Suslov, A V

    1978-01-01

    Analyzes the effects of catalysts on the heterogeneous oxidation of coal in deflagration processes of stoichiometric mixtures. The following substances are studied as catalysts: alkali and alkaline-earth metals, and compounds of copper, lead, chromium, iron, and sulfur. In the first case the catalysts are used in the form of nitrates and the nitrate simultaneously plays the role of an oxidizer. In the second case the catalysts are added to stoichiometric mixtures of ammonium nitrate with carbon. It is shown that during carbon oxidation by nitrates the catalytic efficiency of the metals studied forms the following order: sodium > lead > potassium > barium > aluminium > calcium > magnesium > copper. The calculated and experimental parameters of combustion are given. The problem of dependence of combustion rate on combustion heat, the mechanism of the combustion reaction and the catalytic effects of the additives are discussed. Features of heterogeneous catalysis in the oxidation process of carbon by various oxidizers are analyzed. The investigations on the combustion process are important as the process takes place during explosion of coal dust in underground coal mines and during burning of coal in industrial furnaces. (34 refs.) (In Russian)

  8. Metal Phosphate-Supported Pt Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Xiaoshuang Qian

    2014-12-01

    Full Text Available Oxides (such as SiO2, TiO2, ZrO2, Al2O3, Fe2O3, CeO2 have often been used to prepare supported Pt catalysts for CO oxidation and other reactions, whereas metal phosphate-supported Pt catalysts for CO oxidation were rarely reported. Metal phosphates are a family of metal salts with high thermal stability and acid-base properties. Hydroxyapatite (Ca10(PO46(OH2, denoted as Ca-P-O here also has rich hydroxyls. Here we report a series of metal phosphate-supported Pt (Pt/M-P-O, M = Mg, Al, Ca, Fe, Co, Zn, La catalysts for CO oxidation. Pt/Ca-P-O shows the highest activity. Relevant characterization was conducted using N2 adsorption-desorption, inductively coupled plasma (ICP atomic emission spectroscopy, X-ray diffraction (XRD, transmission electron microscopy (TEM, CO2 temperature-programmed desorption (CO2-TPD, X-ray photoelectron spectroscopy (XPS, and H2 temperature-programmed reduction (H2-TPR. This work furnishes a new catalyst system for CO oxidation and other possible reactions.

  9. Radiation modification of vanadium catalyst for anthracene oxidation

    International Nuclear Information System (INIS)

    Norek, J.; Vymetal, J.; Mucka, V.; Pospisil, M.; Cabicar, J.

    1985-01-01

    Vanadium pentoxide on a suitable carrier is often used as catalyst for the oxidation of anthracene in the gaseous phase to 9,10-anthraquinone. The activity and selectivity of the catalyst may be affected by irradiation. The effects were studied of gamma radiation on the properties of the catalyst where the active system was a V 2 O 5 -KOH-K 2 SO 4 mixture on a Al 2 O 3 +SiO 2 carrier. The 60 Co radiation source had an activity of 185 TBq; the carrier of the catalyst was irradiated at a dose rate of 3.05, 1.98 and 0.084 kGy/h to a total dose of 10 kGy. Irradiation increased the selectivity of the catalyst such that in the oxidation temperature optimum of 300 to 400 degC the yield of 9,10-anthraquinone increased by 4.6 to 4.8 %mol. to roughly 90 %mol.; a significant reduction of the content of acid components (phthalanhydride) in the oxidation product also occurred. This effect remained unchanged for 5 months after irradiation. A reduction of selectivity was observed at lower dose rates only in the temperature range between 400 and 480 degC. (A.K.)

  10. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  11. Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

    Energy Technology Data Exchange (ETDEWEB)

    Que, Jr., Lawrence [Univ. of Minnesota, Minneapolis, MN (United States)

    2016-03-22

    Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

  12. Chemical nature of catalysts of oxide nanoparticles in environment ...

    Indian Academy of Sciences (India)

    12

    Chemical nature of catalysts of oxide nanoparticles in environment prevailing during growth of carbon nanostructures by CCVD. M. Jana*, A. Sil and S. Ray. †. Department of Metallurgical and Materials Engineering. Indian Institute of Technology Roorkee. Roorkee 247 667, India. Present address: *School of Materials ...

  13. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni A.

    2014-01-01

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses

  14. Sol-gel based oxidation catalyst and coating system using same

    Science.gov (United States)

    Watkins, Anthony N. (Inventor); Leighty, Bradley D. (Inventor); Oglesby, Donald M. (Inventor); Patry, JoAnne L. (Inventor); Schryer, Jacqueline L. (Inventor)

    2010-01-01

    An oxidation catalyst system is formed by particles of an oxidation catalyst dispersed in a porous sol-gel binder. The oxidation catalyst system can be applied by brush or spray painting while the sol-gel binder is in its sol state.

  15. Catalysts with Cu base supported in mixed oxides to generate H2: reformed of methanol in oxidant atmosphere

    International Nuclear Information System (INIS)

    Aguila M, M.M.; Perez H, R.; Rodriguez L, V.

    2006-01-01

    In this work, the characterization of Cu supported in CeO 2 -ZrO 2 , for to generate H 2 starting from the one reformed of methanol with water vapor and oxygen is presented. The sol-gel technique and classic impregnation for the obtaining of the supports and catalysts respectively were used. The materials were characterized by XRD, SEM, adsorption- desorption of N 2 and TPR. The catalytic materials presented crystalline phases associated with the zircon (tetragonal and monoclinic phase) and the ceria (cubic phase) depending on the CeO 2 /ZrO 2 relationship. The morphology of the catalysts was analyzed by SEM being observed semispheric particles for the rich materials in ZrO 2 and added planars in the rich materials in CeO 2 . The ceria addition to the zircon favors the specific area of the mixed oxides CeO 2 -ZrO 2 and it promotes the reducibility of the copper oxide at low temperatures. The rich catalysts in ceria also showed high activity in the methanol transformation and bigger selectivity toward the production of H 2 . This result is associated with the presence of copper species that decrease to low temperature present in the rich catalysts in ceria and that they are not present in the rich catalysts in zircon. (Author)

  16. Redox Equilibria in SO2 Oxidation Catalysts

    DEFF Research Database (Denmark)

    Rasmussen, Søren Birk; Eriksen, Kim Michael; Boghosian, Soghomon

    1999-01-01

    been carried out regarding the complex and compound formation of V(V) and the formation of V(IV) and V(III) compounds with low solubility causing catalyst deactivation. However, the redox chemistry of vanadium and the complex formation of V(IV) is much less investigated and further information...... on these subjects in pyrosulfate melts is needed to obtain a deeper understanding of the reaction mechanism. The present paper describes our efforts so far to study the V(IV) chemistry using especially spectroscopic and electrochemical methods....

  17. Oxidative dehydrogenation of ethylbenzene using nitrous oxide over vanadia-magnesia catalysts

    NARCIS (Netherlands)

    Shiju, N.R.; Anilkumar, M.; Gokhale, S.P.; Rao, B.S.; Satyanarayana, C.V.V.

    2011-01-01

    A series of V-Mg-O catalysts with different loadings of vanadia were prepared by the wet impregnation method and the effect of the local structure of these catalysts on the oxidative dehydrogenation of ethylbenzene with N2O was investigated. High styrene selectivity (97%) was obtained at 773 K. The

  18. Mechanism of 1, 1-d2 propene oxidation over oxide catalysts

    International Nuclear Information System (INIS)

    Portefaix, J.L.; Figueras, F.; Forissier, M.

    1980-01-01

    CD 2 CHCH 3 was oxidized over bismuth molybdate, tin-antimony mixed oxides and supported molybdenum and vanadium oxide catalysts. The deuterium retention is high ( > 90%) in the recovered propene. Percentage retentions of deuterium in the acrolein agree with literature data when bismuth molybdate is used as catalyst. On Sb-Sn-O and supported Mo and V oxides, no isotope effect is noticed for the abstraction of the second hydrogen from the olefin. The slow step of the reaction may therefore be different for the oxidation of propene on Bi-Mo-O and Sb-Sn-O. The ethanal produced by oxidation of CD 2 CHCH 3 contains only minor amounts of deuterium, whatever the catalyst used. It is suggested that partial oxidation of propene to acrolein and C-C bond rupture are parallel reactions which involve different intermediates. Possible mechanisms adapted from organic chemistry are presented to explain these findings. 4 tables

  19. Hydroformylation of 1-Hexene over Rh/Nano-Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Sari Suvanto

    2013-03-01

    Full Text Available The effect of nanostructured supports on the activity of Rh catalysts was studied by comparing the catalytic performance of nano- and bulk-oxide supported Rh/ZnO, Rh/SiO2 and Rh/TiO2 systems in 1-hexene hydroformylation. The highest activity with 100% total conversion and 96% yield of aldehydes was obtained with the Rh/nano-ZnO catalyst. The Rh/nano-ZnO catalyst was found to be more stable and active than the corresponding rhodium catalyst supported on bulk ZnO. The favorable morphology of Rh/nano-ZnO particles led to an increased metal content and an increased number of weak acid sites compared to the bulk ZnO supported catalysts. Both these factors favored the improved catalytic performance. Improvements of catalytic properties were obtained also with the nano-SiO2 and nano-TiO2 supports in comparison with the bulk supports. All of the catalysts were characterized by scanning electron microscope (SEM, inductively coupled plasma mass spectrometry (ICP-MS, BET, powder X-ray diffraction (PXRD and NH3- temperature-programmed desorption (TPD.

  20. Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

    Science.gov (United States)

    Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

    2018-04-13

    Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

  1. Process for Making a Noble Metal on Tin Oxide Catalyst

    Science.gov (United States)

    Davis, Patricia; Miller, Irvin; Upchurch, Billy

    2010-01-01

    To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-01

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

  3. Pretreatment of Platinum/Tin Oxide-Catalyst

    Science.gov (United States)

    Hess, Robert V.; Paulin, Patricia A.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M.; Upchurch, Billy T.; Brown, Kenneth G.

    1987-01-01

    Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

  4. High-throughput technology for novel SO2 oxidation catalysts

    International Nuclear Information System (INIS)

    Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

    2011-01-01

    We review the state of the art and explain the need for better SO 2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO 2 to SO 3 . High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO 2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO 2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO 3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. (topical review)

  5. Comparison of direct and indirect plasma oxidation of NO combined with oxidation by catalyst

    DEFF Research Database (Denmark)

    Jogi, Indrek; Stamate, Eugen; Irimiea, Cornelia

    2015-01-01

    of the DBD reactor decreased the long-term efficiency of direct plasma oxidation. At the same time, the efficiency of indirect oxidation increased at elevated reactor temperatures. Additional experiments were carried out to investigate the improvement of indirect oxidation by the introduction of catalyst...

  6. Electrical conductivity of uranium-antimony oxide catalysts

    International Nuclear Information System (INIS)

    Golunski, S.E.; Nevell, T.G.; Hucknall, D.J.

    1985-01-01

    The relative ionic and electronic contributions to the electrical conductivity of a uranium-antimony oxide catalyst and of USbO 5 have been determined from measurements of a.c. and d.c. conductance. Under inert atmospheres (390 to 775 K) conduction in the catalyst (predominantly USb 3 O 10 together with small proportions of Sb 2 O 4 and USbO 5 ) is associated with both electronic and effectively charged atomic point defects. Only electronic conduction occurs in USbO 5 . Under oxygen (10 to 70 kPa, 493 to 682 K) both materials are n-type semiconductors at higher temperatures, but at lower temperatures semiconducting behaviour varies with the pressure of oxygen. Heating USbO 5 in oxygen induces an ionic contribution to conductivity. Ionic conduction in the catalyst is eliminated by heating in hydrogen or propene at 470 K but is restored by heating in oxygen. It is suggested that both charged oxygen vacancies and interstitial oxide ions are involved in interactions of gaseous components with uranium-antimony oxides. With alkenes, interstitial oxide ions give rise to the products of selective partial oxidation. (author)

  7. Electrical conductivity of uranium-antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Golunski, S.E.; Nevell, T.G. (Portsmouth Polytechnic (UK)); Hucknall, D.J. (Southampton Univ. (UK). Dept. of Chemistry)

    1985-05-01

    The relative ionic and electronic contributions to the electrical conductivity of a uranium-antimony oxide catalyst and of USbO/sub 5/ have been determined from measurements of a.c. and d.c. conductance. Under inert atmospheres (390 to 775 K) conduction in the catalyst (predominantly USb/sub 3/O/sub 10/ together with small proportions of Sb/sub 2/O/sub 4/ and USbO/sub 5/) is associated with both electronic and effectively charged atomic point defects. Only electronic conduction occurs in USbO/sub 5/. Under oxygen (10 to 70 kPa, 493 to 682 K) both materials are n-type semiconductors at higher temperatures, but at lower temperatures semiconducting behaviour varies with the pressure of oxygen. Heating USbO/sub 5/ in oxygen induces an ionic contribution to conductivity. Ionic conduction in the catalyst is eliminated by heating in hydrogen or propene at 470 K but is restored by heating in oxygen. It is suggested that both charged oxygen vacancies and interstitial oxide ions are involved in interactions of gaseous components with uranium-antimony oxides. With alkenes, interstitial oxide ions give rise to the products of selective partial oxidation.

  8. Pd enhanced WC catalyst to promote heterogeneous methane combustion

    International Nuclear Information System (INIS)

    Terracciano, Anthony Carmine; De Oliveira, Samuel; Siddhanti, Deepti; Blair, Richard; Vasu, Subith S.; Orlovskaya, Nina

    2017-01-01

    Highlights: • Pd enhanced WC catalyst particles were synthesized via mechanochemical alloying. • Catalyst was characterized by XRD, XRF, SEM, and EDS. • Catalyst was deposited on porous ZrO_2 and evaluated in heterogeneous combustion. • During combustion temperature profiles and spectral emissions were collected. - Abstract: The efficiency of combustion for low cost heat production could be greatly enhanced if an active and low cost catalyst would be used to facilitate the chemical reactions occurring during combustor operation. Within this work an experimental study of palladium (Pd) enhanced tungsten carbide (WC) catalyst, synthesized via high energy ball milling and deposited by dip coating onto a magnesia partially stabilized zirconia (MgO-ZrO_2) porous matrix of 10 ppin was evaluated in heterogeneous methane combustion. The synthesized powder was characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectroscopy (EDS) analysis, as well as by X-ray Fluorescence (XRF); and the morphology of the deposited WC-Pd coating was also characterized using SEM and EDS. Performance evaluation of the heterogeneous combustor with WC-Pd coated MgO-ZrO_2 porous media was conducted at constant air flow rate and various equivalence ratios of methane/air gaseous mixtures, while monitoring axial temperature profiles within the combustion chamber using thermocouples, as well as thermal radiative and acoustic emissions from the combustor exhaust using an externally placed CCD camera and a microphone. It was found that there is a strong dependence of flame position and maximum temperature on equivalence ratio (φ) over the range of 0.47 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02. Additionally it was found that over the same equivalence ratio range, there is a characteristic 4 peak acoustic signature between 200 and 500 Hz. It was found that at higher equivalence ratios 0.51 ± 0.02 ⩽ φ ⩽ 0.75 ± 0.02 the performance of combustor

  9. The role of potassium as a promoter in iron catalysts for ammonia synthesis

    NARCIS (Netherlands)

    Altenburg, K.; Bosch, H.; van Ommen, J.G.; Gellings, P.J.

    1980-01-01

    Five ammonia synthesis catalysts, mainly differing in potassium content, were prepared from a commercial doubly promoted iron catalyst. The activities of these catalysts were measured at 350–450 °C and 5–200 atm. The experimental reaction rates were fitted to the modified Temkin rate equation.

  10. Heteropoly acid promoted Cu and Fe catalysts for the selective catalytic reduction of NO with ammonia

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Mossin, Susanne L.; Riisager, Anders

    2011-01-01

    Cu/TiO2, Fe/TiO2 and heteropoly acid promoted Cu/TiO2, Fe/TiO2 catalysts were prepared and characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR and EPR. The catalysts exhibited only crystalline TiO2 phases with the active metals and promoters in highly dispersed state. The acidic properties...... activity and acidity was lower for promoted catalysts than for unpromoted catalysts. In the heteropoly acid promoted catalysts the SCR active Cu and Fe metals were protected from potassium poisons by bonding of the potassium to the Brønsted acid centres. Thus heteropoly acid promoted catalysts might...... be suitable for biomass fired power plant SCR applications....

  11. Progress on the mechanistic understanding of SO2 oxidation catalysts

    DEFF Research Database (Denmark)

    Lapina, Olga B.; Bal'zhinimaev, B.S.; Boghosian, Soghomon

    1999-01-01

    Production, Goskhimizdat (in Russian), Moscow, 1954, p. 348]. In recent years these catalysts have also been used to clean flue gases and other SO; containing, industrial off-gases. In spite of the importance and long utilization of these industrial processes, the catalytic active species and the reaction......For almost a century vanadium oxide based catalysts have been the dominant materials in industrial processes for sulfuric acid production. A vast body of information leading to fundamental knowledge on the catalytic process was obtained by Academician [G.K. Boreskov, Catalysis in Sulphuric Acid...... mechanism. A multiinstrumental investigation that combine the efforts of four groups from four different countries has been carried out on the model system as well as on working industrial catalysts. Detailed information has been obtained on the complex and on the redox chemistry of vanadium. Based on this...

  12. Ir catalysts: Preventing CH3COOH formation in ethanol oxidation

    Science.gov (United States)

    Miao, Bei; Wu, Zhipeng; Xu, Han; Zhang, Minhua; Chen, Yifei; Wang, Lichang

    2017-11-01

    Current catalysts used for ethanol oxidation reaction (EOR) cannot effectively prevent CH3COOH formation, and thus become a major hindrance for direct ethanol fuel cell applications. We report an Ir catalyst that shows great promise for a complete EOR based on density functional theory calculations using PBE functional. The reaction barrier on Ir(1 0 0) was found to be 2.10 eV for CH3COOH formation, which is much higher than currently used Pd and Pt, and 0.57 eV for Csbnd C bond cleavage in CHCO species, which are comparable to Pd and Pt. The result suggests future directions for studying optimal complete EOR catalysts.

  13. Mitigation of hydrogen by oxidation using nitrous oxide and noble metal catalysts

    International Nuclear Information System (INIS)

    Britton, M.D.

    1995-01-01

    This test studied the ability of a blend of nuclear-grade, noble-metal catalysts to catalyze a hydrogen/nitrous oxide reaction in an effort to mitigate a potential hydrogen (H 2 ) gas buildup in the Hanford Site Grout Disposal Facility. For gases having H 2 and a stoichiometric excess of either nitrous oxide or oxygen, the catalyst blend can effectively catalyze the H 2 oxidation reaction at a rate exceeding 380 μmoles of H 2 per hour per gram of catalyst (μmol/h/g) and leave the gas with less than a 0.15 residual H 2 Concentration. This holds true in gases with up to 2.25% water vapor and 0.1% methane. This should also hold true for gases with up to 0.1% carbon monoxide (CO) but only until the catalyst is exposed to enough CO to block the catalytic sites and stop the reaction. Gases with ammonia up to 1% may be slightly inhibited but can have reaction rates greater than 250 μmol/h/g with less than a 0.20% residual H 2 concentration. The mechanism for CO poisoning of the catalyst is the chemisorption of CO to the active catalyst sites. The CO sorption capacity (SC) of the catalyst is the total amount of CO that the catalyst will chemisorb. The average SC for virgin catalyst was determined to be 19.3 ± 2.0 μmoles of CO chemisorbed to each gram of catalyst (μmol/g). The average SC for catalyst regenerated with air was 17.3 ± 1.9 μmol/g

  14. Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol.

    Science.gov (United States)

    Zhang, Jie; Zhang, Changbin; He, Hong

    2015-09-01

    OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO4 (OMS-2-SO4) and Mn(CH3COO)2 (OMS-2-AC) as precursors. SO4(2-)-doped OMS-2-AC catalysts with different SO4(2-) concentrations were prepared next by adding (NH4)2SO4 solution into OMS-2-AC samples to investigate the effect of the anion SO4(2-) on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO4(2-) doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO4(2-) (SO4/catalyst=0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO4(2-) species in the OMS-2-AC catalyst could decrease the Mn-O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO4(2-) species in OMS-2-SO4 samples. Copyright © 2015. Published by Elsevier B.V.

  15. 'Methane oxidation on supported gold catalysts'

    DEFF Research Database (Denmark)

    Walther, Guido

    2008-01-01

    steady-state activity measurements were performed to obtain the reaction rates for CO and H2 oxidation. These reactions were studied on three different gold particle sizes using either O2 or N2O as oxidation agents. Using particle size distributions obtained from TEM analysis, it was found that the CO......Methane (CH4), a major compound of natural gas, has been suggested as a future energy carrier. However, it is also known to be a strong greenhouse gas. The use of CH4 obtained from crude oil as an associated gas is often uneconomical, and it is thus burned off. Avoiding flaring and making...... the energy stored in the molecule available, is a major research challenge. In this PhD thesis, CH4 oxidation on nanoparticular gold is studied both experimentally and theoretically. In the course of this PhD project, CH4 oxidation was experimentally found more likely to form CO2 and H2O than other low index...

  16. Thermally oxidized aluminum as catalyst-support layer for vertically aligned single-walled carbon nanotube growth using ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Azam, Mohd Asyadi, E-mail: asyadi@jaist.ac.jp [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Fujiwara, Akihiko [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1, Kouto, Sayo-cho, Sayo, Hyogo 679-5198 (Japan); Shimoda, Tatsuya [School of Materials Science, Japan Advanced Institute of Science and Technology (JAIST), 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

    2011-11-01

    Characteristics and role of Al oxide (Al-O) films used as catalyst-support layer for vertical growth of single-walled carbon nanotubes (SWCNTs) were studied. EB-deposited Al films (20 nm) were thermally oxidized at 400 deg. C (10 min, static air) to produce the most appropriate surface structure of Al-O. Al-O catalyst-support layers were characterized using various analytical measurements, i.e., atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and spectroscopy ellipsometry (SE). The thermally oxidized Al-O has a highly roughened surface, and also has the most suitable surface chemical states compared to other type of Al-O support layers. We suggest that the surface of thermally oxidized Al-O characterized in this work enhanced Co catalyst activity to promote the vertically aligned SWCNT growth.

  17. Ammonia synthesis over multi-promoted iron catalysts obtained by high-energy ball-milling

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Jiang, Jianzhong; Mørup, Steen

    1999-01-01

    The feasibility of producing ammonia synthesis catalysts from high-energy ball-milling of a simple mixture of the constituent oxides has been investigated. The effect of ball-milling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show...

  18. New Catalysts for Direct Methanol Oxidation Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Adzic, Radoslav

    1998-08-01

    A new class of efficient electrocatalytic materials based on platinum - metal oxide systems has been synthetized and characterized by several techniques. Best activity was found with NiWO{sub 4}-, CoWO{sub 4}-, and RuO{sub 2}- sr¡pported platinum catalysts. A very similar activity at room temperature was observed with the electrodes prepared with the catalyst obtained from International Fuel Cells Inc. for the same Pt loading. Surprisingly, the two tungstates per se show a small activity for methanol oxidation without any Pt loading. Synthesis of NiWO{sub 4} and CoWO{sub 4} were carried out by solid-state reactions. FTIR spectroscopy shows that the tungstates contain a certain amount of physically adsorbed water even after heating samples at 200{degrees}C. A direct relationship between the activity for methanol oxidation and the amount of adsorbed water on those oxides has been found. The Ru(0001) single crystal shows a very small activity for CO adsorption and oxidation, in contrast to the behavior of polycrystalline Ru. In situ extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray absorption near edge spectroscopy (XANES) showed that the OH adsorption on Ru in the Pt-Ru alloy appears to be the limiting step in methanol oxidation. This does not occur for Pt-RuO{SUB 2} electrocatalyst, which explains its advantages over the Pt-Ru alloys. The IFCC electrocatalyst has the properties of the Pt-Ru alloy.

  19. PILOT TESTING OF MERCURY OXIDATION CATALYSTS FOR UPSTREAM OF WET FGD SYSTEMS

    International Nuclear Information System (INIS)

    Gary M. Blythe

    2002-01-01

    The objective of this project is to demonstrate at pilot scale the use of solid honeycomb catalysts to promote the oxidation of elemental mercury in the flue gas from coal combustion. The project is being funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-01NT41185. EPRI, Great River Energy (GRE), and City Public Service (CPS) of San Antonio are project co-funders. URS Group is the prime contractor. The mercury catalytic oxidation process under development uses catalyst materials applied to honeycomb substrates to promote the oxidation of elemental mercury in the flue gas from coal-fired power plants that have wet lime or limestone flue gas desulfurization (FGD) systems. Oxidized mercury is removed in the wet FGD absorbers and co-precipitates in a stable form with the byproducts from the FGD system. The co-precipitated mercury does not appear to adversely affect the disposal or reuse properties of the FGD byproduct. The current project will test previously identified, effective catalyst materials at a larger, pilot scale and in a commercial form, so as to provide engineering data for future full-scale designs. The pilot-scale tests will continue for up to 14 months at each of two sites to provide longer-term catalyst life data. This is the first full reporting period for the subject Cooperative Agreement. During this period, most of the project efforts were related to project initiation and planning. There is no significant technical progress to report for the current period

  20. The role of promoters for Ni catalysts in low temperature (membrane) steam methane reforming

    NARCIS (Netherlands)

    Ligthart, D.A.J.M.; Pieterse, J.A.Z.; Hensen, E.J.M.

    2011-01-01

    In the search for active and stable Ni-based catalysts for steam methane reforming in membrane reactors, the effect of three different promoters La, B and Rh was compared. Promoted and unpromoted Ni catalysts were characterized by TEM, TPR and X-ray absorption spectroscopy. The average Ni particle

  1. Bi-modified Pd/C catalyst via irreversible adsorption and its catalytic activity for ethanol oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Cai, Jindi; Huang, Yiyin; Guo, Yonglang

    2013-01-01

    Highlights: • Pd-Bi/C catalysts were easily prepared by irreversible adsorption of Bi on Pd/C surface. • The adsorption of Bi increases the oxygen-containing species obviously on Pd-Bi/C surface. • Only a little amount of Bi on Pd-Bi/C can play a significant role in ethanol oxidation reaction (EOR). • Current density of EOR on Pd-Bi/C (20:1) is 2.4 times higher than that on Pd/C. • Anti-poisoning ability and durability of Pd-Bi/C (20:1) is greatly enhanced. -- Abstract: A facile approach to promote ethanol electro-oxidation on Pd-based catalysts is presented by the modification of Bi on Pd/C catalyst via irreversible adsorption. X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) measurements show that the modification of Bi has no significant effect on the Pd morphology and particle size distribution. Bi(III) and Pd(0) are the dominant forms in Pd-Bi/C catalyst. Electrochemical tests show that the modification of the appropriate amount of Bi on Pd/C catalyst can remarkably enhance activity toward ethanol oxidation reaction (EOR) up to about 2.4 times higher compared to Pd/C catalyst. The Pd-Bi/C (20:1) catalyst exhibits excellent stability and enhances CO tolerance. The enhanced electrochemical performance of Pd-Bi/C catalyst is attributed to the electronic effect and the bifunctional mechanism. The high exchange current density and the low apparent activation energy on Pd-Bi/C (20:1) catalyst reveal its faster kinetics and higher intrinsic activity compared to Pd/C catalyst

  2. Oxidation of tritium in packed bed of noble metal catalyst for detritiation from system gases

    International Nuclear Information System (INIS)

    Nishikawa, Masabumi; Takeishi, Toshiharu; Munakata, Kenzo; Kotoh, Kenji; Enoeda, Mikio

    1985-01-01

    Catalytic oxidation rates of tritium in the bed of the noble metal catalysts are obtained and compared with the oxidation rates observed for the packed bed of spongy copper oxide or hopcalites. Use of Pt- or Pd-aluminia catalysts is recommended in this study because they give effective oxidation rates of tritium in the ambient temperature range. The adsorption performance of tritiated water in the catalyst bed is also discussed. (orig.)

  3. Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

    CSIR Research Space (South Africa)

    Makgwane, PR

    2015-03-01

    Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

  4. A mechanistic study on the oxidative coupling of methane over lithium doped magnesium oxide catalysts

    NARCIS (Netherlands)

    Geerts, J.W.M.H.; Kasteren, van J.M.N.; Wiele, van der K.; Imarisio, G.; Frias, M.; Berntgen, J.M.

    1988-01-01

    To elucidate the importance of various reaction steps in the oxidative convers ion of methane, experiments were carried out with three reaction products: ethane, ethylene and carbon monoxide. These products were studied seperately, in oxidation experiments with and without a catalyst. Moreover , the

  5. Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

    Science.gov (United States)

    Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

    2012-05-14

    The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Directory of Open Access Journals (Sweden)

    Ryo eWatanabe

    2013-10-01

    Full Text Available For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1–xSrxFeyMn1–yO3–d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8, perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst with that of an industrial potassium promoted iron (Fe–K catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d and the Fe–K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3–d was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d perovskite oxide.

  7. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  8. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  9. Alkali promotion effect in Fischer-Tropsch cobalt-alumina catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Eliseev, O.L.; Tsapkina, M.V.; Davydov, P.E.; Kazantsev, R.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry; Belousova, O.S.; Lapidus, A.L. [Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation)

    2011-07-01

    Promoting Co-alumina Fischer-Tropsch synthesis catalysts with alkali and alkaline-earth metals was studied. XRD, oxygen titration and CO chemisorption were used for the characterization of the catalysts. The best results in terms of catalyst selectivity and long-chain alkanes content in synthesized products were obtained with K-promoted catalyst. Catalytic performance strongly depends on K:Co atomic ratio as well as preparation procedure. Effect of K loading on selectivities is non-linear with extreme point at K:Co=0.01. Significant increase in C{sub 5+} selectivity of K-promoted catalyst may be explained as a result of strong CO adsorption on the catalyst surface, as was confirmed in CO chemisorption experiments. (orig.)

  10. 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.

  11. Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

    2005-11-15

    This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

  12. Optimization of Cs Content in Co-Mn-Al Mixed Oxide as Catalyst for N2O Decomposition.

    Czech Academy of Sciences Publication Activity Database

    Chromčáková, Ž.; Obalová, L.; Kustrowski, P.; Drozdek, M.; Karásková, K.; Jirátová, Květa; Kovanda, F.

    2015-01-01

    Roč. 41, č. 12 (2015), s. 9319-9332 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Třešť, 16.09.2014-20.09.2014] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : nitrous oxide * mixed oxide catalysts * cesium promoter * layered double hydroxides Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

  13. Electrochemical promotion of catalytic reactions with Pt/C (or Pt/Ru/C)//PBI catalysts

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Bandur, Viktor

    2007-01-01

    The paper is an overview of the results of the investigation on electrochemical promotion of three catalytic reactions: methane oxidation with oxygen, NO reduction with hydrogen at 135 degrees C and Fischer-Tropsch synthesis (FTS) at 170 degrees C in the [CH4/O-2(or NO/H-2 or CO/H-2)/Ar//Pt(or Pt....../Ru)//PBI(H3PO4)/H-2, Ar] fuel cell. It has been shown that the partial methane oxidation to C2H2 and the C-2 selectivity were electrochemically promoted by the negative catalyst polarization. This was also the case in NO reduction with hydrogen for low NO and H-2 partial pressures. In both cases the catalytic...... reactions have been promoted by the electrochemically produced hydrogen. It has been found that the NO reduction with hydrogen on the Pt/PBI strongly depends on NO and hydrogen partial pressures in the working gas mixture. At higher NO and H-2 partial pressures the catalysis is promoted...

  14. Kinetics of the reduction of uranium oxide catalysts

    International Nuclear Information System (INIS)

    Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

    1977-01-01

    The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

  15. Understanding the performance and mechanism of Mg-containing oxides as support catalysts in the thermal dry reforming of methane.

    Science.gov (United States)

    Khairudin, Nor Fazila; Sukri, Mohd Farid Fahmi; Khavarian, Mehrnoush; Mohamed, Abdul Rahman

    2018-01-01

    Dry reforming of methane (DRM) is one of the more promising methods for syngas (synthetic gas) production and co-utilization of methane and carbon dioxide, which are the main greenhouse gases. Magnesium is commonly applied in a Ni-based catalyst in DRM to improve catalyst performance and inhibit carbon deposition. The aim of this review is to gain better insight into recent developments on the use of Mg as a support or promoter for DRM catalysts. Its high basicity and high thermal stability make Mg suitable for introduction into the highly endothermic reaction of DRM. The introduction of Mg as a support or promoter for Ni-based catalysts allows for good metal dispersion on the catalyst surface, which consequently facilitates high catalytic activity and low catalyst deactivation. The mechanism of DRM and carbon formation and reduction are reviewed. This work further explores how different constraints, such as the synthesis method, metal loading, pretreatment, and operating conditions, influence the dry reforming reactions and product yields. In this review, different strategies for enhancing catalytic activity and the effect of metal dispersion on Mg-containing oxide catalysts are highlighted.

  16. Catalyst and method for reduction of nitrogen oxides

    Science.gov (United States)

    Ott, Kevin C [Los Alamos, NM

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  17. Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

    International Nuclear Information System (INIS)

    Cho, Hong-Baek; Lee, Bae Uk; Nakayama, Tadachika; Park, Yeung-Ho; Ryu, Chung-Han

    2013-01-01

    The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps

  18. Uranium oxide catalysts: environmental applications for treatment of chlorinated organic waste from nuclear industry.

    Science.gov (United States)

    Lazareva, Svetlana; Ismagilov, Zinfer; Kuznetsov, Vadim; Shikina, Nadezhda; Kerzhentsev, Mikhail

    2018-02-05

    Huge amounts of nuclear waste, including depleted uranium, significantly contribute to the adverse environmental situation throughout the world. An approach to the effective use of uranium oxides in catalysts for the deep oxidation of chlorine-containing hydrocarbons is suggested. Investigation of the catalytic activity of the synthesized supported uranium oxide catalysts doped with Cr, Mn and Co transition metals in the chlorobenzene oxidation showed that these catalysts are comparable with conventional commercial ones. Physicochemical properties of the catalysts were studied by X-ray diffraction, temperature-programmed reduction with hydrogen (H 2 -TPR), and Fourier transform infrared spectroscopy. The higher activity of Mn- and Co-containing uranium oxide catalysts in the H 2 -TPR and oxidation of chlorobenzene in comparison with non-uranium catalysts may be related to the formation of a new disperse phase represented by uranates. The study of chlorobenzene adsorption revealed that the surface oxygen is involved in the catalytic process.

  19. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  20. Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

    Science.gov (United States)

    Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

    2015-03-20

    A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

  1. Development of New Diesel Oxidation and NH3 Slip Catalysts

    DEFF Research Database (Denmark)

    Hansen, Thomas Klint

    Diesel engines used in the transport sector and for other heavy machinery form pollutants during the combustion process. Emission of these pollutants into the atmosphere has harmful consequences on human health and the environment. In order to mitigate these harmful effects, regulations have been...... imposed by environmental protection agencies on the most significant pollutants, including CO, hydrocarbons, NOx, and particulate matter. To reduce emissions to the levels specified by the recent Euro VI regulations, it is necessary to apply catalytic exhaust gas aftertreat-ment systems. A modern diesel...... exhaust aftertreatment system commonly consists of a Pt-based diesel oxidation catalyst (DOC) to oxidize CO and unburnt hydrocarbons to CO2 and H2O, and oxidize NO to NO2. This is followed by the diesel particulate filter (DPF), which entraps particulate matter from the exhaust gas. A solution of urea...

  2. Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi

    2014-01-01

    Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

  3. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang

    2018-04-04

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  4. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

    2018-01-01

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  5. Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: Effect of calcination temperature of catalysts

    International Nuclear Information System (INIS)

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-01-01

    Highlights: ► Oxidative desulfurization was studied with WO x /ZrO 2 calcined at different temp. ► The importance of the phases of zirconia and tungsten oxide was suggested. ► The catalyst was analyzed thoroughly with Raman and XRD techniques. ► The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO x /ZrO 2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO x /ZrO 2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO 2 ) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO 3 and monoclinic ZrO 2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO x /ZrO 2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

  6. Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst.

    Science.gov (United States)

    Stevanović, Dragana; Pejović, Anka; Damljanović, Ivan; Minić, Aleksandra; Bogdanović, Goran A; Vukićević, Mirjana; Radulović, Niko S; Vukićević, Rastko D

    2015-04-30

    In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-D-glucal and 6-deoxy-3,4-di-O-acetyl-L-glucal (3,4-di-O-acetyl-L-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol(-1)) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio α/β=4.129 in the case of peracetylated D-glucal and 8.740 in the case of L-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'α-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M

    2002-01-01

    The molten salts M2S2O7 and MHSO4, the binary molten salt Systems M2S2O7-MHSO4 and the molten salt-gas systems M2S2O7 V2O5 and M2S2O7-M2SO4 V2O5 (M = Na, K, Rb, Cs) in O-2, SO2 and At atmospheres have been investigated by thermal methods like calorimetry, Differential Enthalpic Analysis (DEA) and...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  8. Oxidative desulfurization of synthetic diesel using supported catalysts. Part 3. Support effect on vanadium-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cedeno-Caero, Luis; Gomez-Bernal, Hilda; Fraustro-Cuevas, Adriana; Guerra-Gomez, Hector D.; Cuevas-Garcia, Rogelio [UNICAT, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria 04510, Mexico D.F. (Mexico)

    2008-04-15

    Oxidesulfurization (ODS) of benzothiophenic compounds prevailing in diesel was conducted with hydrogen peroxide in presence of various catalysts, using a model diesel and actual diesel fuel. ODS activities of dibenzothiophenes (DBTs) in hexadecane for a series of V{sub 2}O{sub 5} catalysts supported on alumina, titania, ceria, niobia and silica, were evaluated. Results show that the oxidation activity of DBTs depends on the support used. It was observed that the sulfone yield is not proportional to textural properties or V content. For all catalysts, ODS of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) decreased in the following order: DBT > 4-MDBT > 4,6-DMDBT > BT. This trend does not depend on the catalyst used or the textural properties of the catalysts and supports. In presence of indole ODS activities diminish, except with catalysts supported on alumina-titania mixed oxide, whereas with V{sub 2}O{sub 5}/TiO{sub 2} catalyst the performance is the highest. ODS of Mexican diesel fuel was carried out in presence of this catalyst and S level was diminished in about 99%. (author)

  9. Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

    DEFF Research Database (Denmark)

    Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

    2011-01-01

    Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9) w...

  10. Sulfidation of alumina-supported iron and iron-molybdenum oxide catalysts

    NARCIS (Netherlands)

    Ramselaar, W.L.T.M.; Crajé, M.W.J.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Kraan, van der A.M.

    1990-01-01

    The transition of alumina-supported iron and iron-molybdenum catalysts from the oxidic precursor to the sulfided catalysts was systematically studied by means of in-situ Mössbauer spectroscopy at room temperature. This enabled the adjudgement of various sulfidic phases in the sulfided catalysts. The

  11. Low-temperature conversion of ammonia to nitrogen in water with ozone over composite metal oxide catalyst.

    Science.gov (United States)

    Chen, Yunnen; Wu, Ye; Liu, Chen; Guo, Lin; Nie, Jinxia; Chen, Yu; Qiu, Tingsheng

    2018-04-01

    As one of the most important water pollutants, ammonia nitrogen emissions have increased year by year, which has attracted people's attention. Catalytic ozonation technology, which involves production of ·OH radical with strong oxidation ability, is widely used in the treatment of organic-containing wastewater. In this work, MgO-Co 3 O 4 composite metal oxide catalysts prepared with different fabrication conditions have been systematically evaluated and compared in the catalytic ozonation of ammonia (50mg/L) in water. In terms of high catalytic activity in ammonia decomposition and high selectivity for gaseous nitrogen, the catalyst with MgO-Co 3 O 4 molar ratio 8:2, calcined at 500°C for 3hr, was the best one among the catalysts we tested, with an ammonia nitrogen removal rate of 85.2% and gaseous nitrogen selectivity of 44.8%. In addition, the reaction mechanism of ozonation oxidative decomposition of ammonia nitrogen in water with the metal oxide catalysts was discussed. Moreover, the effect of coexisting anions on the degradation of ammonia was studied, finding that SO 4 2- and HCO 3 - could inhibit the catalytic activity while CO 3 2- and Br - could promote it. The presence of coexisting cations had very little effect on the catalytic ozonation of ammonia nitrogen. After five successive reuses, the catalyst remained stable in the catalytic ozonation of ammonia. Copyright © 2017. Published by Elsevier B.V.

  12. Promoted V2O5/TiO2 catalysts for selective catalytic reduction of NO with NH3 at low temperatures

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Schill, Leonhard; Godiksen, Anita

    2016-01-01

    characterized by N2 physisorption, XRPD, NH3-TPD, H2-TPR, Raman, FTIR and EPR spectroscopy to investigate the properties of the catalysts. XRPD, Raman and FTIR showed that promotion with 15 wt.% HPA does not cause V2O5 to be present in crystalline form, also at a loading of 5 wt.% V2O5. Hence, use of HPAs does......The influence of varying the V2O5 content (3–6 wt.%) was studied for the selective catalytic reduction (SCR) of nitrogen oxides by ammonia on heteropoly acid (HPA)- and tungsten oxide (WO3)-promoted V2O5/TiO2 catalysts. The SCR activity and alkali deactivation resistance of HPA-promoted V2O5/TiO2...... catalysts was found to be much higher than for WO3-promoted catalysts. By increasing the vanadium content from 3 to 5 wt.% the catalysts displayed a two fold increase in activity at 225 °C and retained their initial activity after alkali doping at a molar K/V ratio of 0.181. Furthermore, the catalysts were...

  13. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  14. An oxidation-resistant indium tin oxide catalyst support for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Chhina, H.; Campbell, S. [Ballard Power Systems Inc., 9000 Glenlyon Parkway, Burnaby, BC V5J 5J8 (Canada); Kesler, O. [Department of Mechanical Engineering, University of British Columbia, Vancouver, BC, V6T 1Z4 (Canada)

    2006-10-27

    The oxidation of carbon catalyst supports causes degradation in catalyst performance in proton exchange membrane fuel cells (PEMFCs). Indium tin oxide (ITO) is considered as a candidate for an alternative catalyst support. The electrochemical stability of ITO was studied by use of a rotating disk electrode (RDE). Oxidation cycles between +0.6 and +1.8V were applied to ITO supporting a Pt catalyst. Cyclic voltammograms (CVs) both before and after the oxidation cycles were obtained for Pt on ITO, Hispec 4000 (a commercially available catalyst), and 40wt.% Pt dispersed in-house on Vulcan XC-72R. Pt on ITO showed significantly better electrochemical stability, as determined by the relative change in electrochemically active surface area after cycling. Hydrogen desorption peaks in the CVs existed even after 100 cycles from 0.6 to 1.8V for Pt on ITO. On the other hand, most of the active surface area was lost after 100 cycles of the Hispec 4000 catalyst. The 40wt.% Pt on Vulcan made in-house also lost most of its active area after only 50 cycles. Pt on ITO was significantly more electrochemically stable than both Hispec 4000 and Pt on Vulcan XC-72R. In this study, it was found that the Pt on ITO had average crystallite sizes of 13nm for Pt and 38nm for ITO. Pt on ITO showed extremely high thermal stability, with only {approx}1wt.% loss of material for ITO versus {approx}57wt.% for Hispec 4000 on heating to 1000{sup o}C. The TEM data show Pt clusters dispersed on small crystalline ITO particles. The SEM data show octahedral shaped ITO particles supporting Pt. (author)

  15. Total oxidation of toluene over calcined trimetallic hydrotalcites type catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Palacio, Luz A. [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Grupo Catalizadores y Adsorbentes, Universidad de Antioquia 1-317, A.A. 1226 Medellin (Colombia); Velasquez, Juliana; Echavarria, Adriana [Grupo Catalizadores y Adsorbentes, Universidad de Antioquia 1-317, A.A. 1226 Medellin (Colombia); Faro, Arnaldo [Departamento de Fisicoquimica, Instituto de Quimica, Universidade Federal do Rio de Janeiro, Ilha do Fundao, CT bloco A, Rio de Janeiro (Brazil); Ramoa Ribeiro, F. [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Ribeiro, M. Filipa, E-mail: filipa.ribeiro@ist.utl.pt [Instituto Superior Tecnico, IBB - Centro de Engenharia Biologica e Quimica, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

    2010-05-15

    Two trimetallic ZnCuAl and MnCuAl hydrotalcites have been successfully synthesized by a co-precipitation method. The manganese based material was identified as a new hydrotalcite phase. Both lamellar precursors were calcined at 450 and 600 deg. C and the resulting catalysts were tested on reaction of total oxidation of toluene. The solids were characterized by X-ray diffraction, thermal analysis, atomic absorption spectroscopy, Fourier transformed infrared spectroscopy, N{sub 2} adsorption and H{sub 2} temperature-programmed reduction. It was found that ZnCuAl materials are composed of copper and zinc oxides supported on alumina; while MnCuAl ones comprise basically spinel phases, which were not completely identified. The catalytic behavior of the calcined samples showed that Mn hydrotalcite calcined at 450 deg. C exhibited the best catalytic performance that corresponds to 100% toluene conversion into CO{sub 2} at about 300 deg. C.

  16. Structure and activity of tellurium-cerium oxide acrylonitrile catalysts

    International Nuclear Information System (INIS)

    Bart, J.C.J.; Giordano, N.

    1982-01-01

    Ammoxidation of propylene to acrylonitrile (ACN) was investigated over various silica-supported (Te,Ce)O catalysts at 360 and 440 0 C. The binary oxide system used consists of a single nonstoichiometric fluorite-type phase α-(Ce,Te)O 2 up to about 80 mole% TeO 2 and a tellurium-saturated solid solution β-(Ce,Te)O 2 at higher tellurium concentrations. The ACN yield varies almost linearly with the tellurium content of (Ce,Te)O 2 . The β-(Ce,Te)O 2 phase is the most active component of the system (propylene conversion and ACN selectivity at 440 C of 76.7 and 74%, respectively) and is slightly more selective to ACN than α-Te0 2 . Tellurium reduces the overoxidation properties of cerium and selective oxidation occurs through Te(IV)-bonded oxygen

  17. Total oxidation of toluene over calcined trimetallic hydrotalcites type catalysts

    International Nuclear Information System (INIS)

    Palacio, Luz A.; Velasquez, Juliana; Echavarria, Adriana; Faro, Arnaldo; Ramoa Ribeiro, F.; Ribeiro, M. Filipa

    2010-01-01

    Two trimetallic ZnCuAl and MnCuAl hydrotalcites have been successfully synthesized by a co-precipitation method. The manganese based material was identified as a new hydrotalcite phase. Both lamellar precursors were calcined at 450 and 600 deg. C and the resulting catalysts were tested on reaction of total oxidation of toluene. The solids were characterized by X-ray diffraction, thermal analysis, atomic absorption spectroscopy, Fourier transformed infrared spectroscopy, N 2 adsorption and H 2 temperature-programmed reduction. It was found that ZnCuAl materials are composed of copper and zinc oxides supported on alumina; while MnCuAl ones comprise basically spinel phases, which were not completely identified. The catalytic behavior of the calcined samples showed that Mn hydrotalcite calcined at 450 deg. C exhibited the best catalytic performance that corresponds to 100% toluene conversion into CO 2 at about 300 deg. C.

  18. Secondary promoters in alumina-supported nickel-molybdenum hydroprocessing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, J.M.

    1992-01-01

    Two secondary promoters, phosphorus and fluoride, have been investigated for their influences on the physicochemical properties of alumina-supported nickel-molybdenum hydroprocessing catalysts. Model compound reactions and infrared spectroscopy were used to probe the functionalities of the different catalysts, and the catalysts were tested in the hydroprocessing of a low-nitrogen and a high-nitrogen (quinoline-spiked) gas oil feed to assess the utility of the model compound reaction studies. Fluoride-promoted catalysts with high cumene hydrocracking activity and with comparable thiophene hydrodesulphurization (HDS) activity to Ni-Mo/Al[sub 2]O[sub 3] can be prepared by coimpregnation of the F, Ni and Mo additives. Fluoride promotes the hydrogenation (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing (HYD) and HDS activity of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of a low-nitrogen feed. Fluoride promotes the quinoline hydrodenitrogenation (HDN) activity of Ni-Mo/Al[sub 2]O[sub 3] catalysts. Impregnation of phosphorus prior to the metal additives results in catalysts which are more active in HDS. Phosphorus increases indirectly the Broensted acidity of the catalyst by increasing the activity of the MoS[sub 2]-associated acid sites. Phosphorus promotes the HDSW and HYD activities of Ni-Mo/Al[sub 2]O[sub 3] in the hydroprocessing of the low-N feed. A promotional effect of phosphorus is seen in quinoline HDN. P- and F-promoted Ni-MO/Al[sub 2]O[sub 3] catalysts are very active in quinoline HDN and maintain good activity in HDS and HYD of the high-N feed. Thiophene HDS was a good reaction for probing the activity of catalysts in the HDS of sterically-unhindered molecules, but an inaccurate probe for the HDS of hindered compounds.

  19. Lithium chemistry of lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

    NARCIS (Netherlands)

    Korf, S.J.; Roos, J.A.; de Bruijn, N.A.; van Ommen, J.G.; Ross, J.R.H.

    1990-01-01

    Active sites are created on the surface of a Li/MgO catalyst used for the selective oxidation of methane by the gradual loss of carbon dioxide from surface carbonate species in the presence of oxygen. Decomposition of the carbonate species in the absence of oxygen is detrimental to the activity of

  20. Selective oxidation of methane to ethane and ethylene over various oxide catalysts

    NARCIS (Netherlands)

    Roos, J.A.; Bakker, A.G.; Bosch, H.; van Ommen, J.G.; Ross, J.R.H.

    1987-01-01

    Preliminary results are reported for the oxidative coupling of methane to give ethane/ethylene mixtures over a series of different catalyst formulations; the temperature range studied is 650–850°C. A comparison is made of the behaviour of lead/alumina and lithium/magnesia materials. It is found that

  1. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  2. Use of Graphite Oxide and Graphene Oxide as Catalysts in the Synthesis of Dipyrromethane and Calix[4]pyrrole

    Directory of Open Access Journals (Sweden)

    Sweta Mishra

    2011-08-01

    Full Text Available Graphite oxide and graphene oxides have been used as solid catalysts for the synthesis of 5,5-dialkyldipyrromethanes and calix[4]pyrroles in organic and aqueous solutions at room temperature.

  3. Potassium/calcium/nickel oxide catalysts for the oxidative coupling of methane

    NARCIS (Netherlands)

    Dooley, K.; Dooley, Kerry M.; Ross, J.R.H.; Ross, Julian R.H.

    1992-01-01

    A series of potassium/calcium/nickel oxides were tested for the oxidative coupling of methane (OCM) at 843–943 K and water addition to the feed at 0–66 mol-%. The K/Ni ratios varied from 0.0–0.6 and Ca/Ni from 0.0–11; catalysts with no nickel were also tested. At least 10% water in the feed and

  4. Effect of additives on lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

    NARCIS (Netherlands)

    Korf, S.J.; Roos, J.A.; Veltman, L.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    It has been found that it is possible to improve the activity and stability for the oxidative coupling of methane of a Li/MgO catalyst by the addition of small amounts of the oxides of various transition and rare earth metals. A number of these additives, e.g. SnO2, TiO2, Dy2O3 and Tb4O7, caused

  5. Titania Supported Co-Mn-Al Oxide Catalysts in Total Oxidation of Ethanol

    Czech Academy of Sciences Publication Activity Database

    Ludvíková, Jana; Jirátová, Květa; Klempa, Jan; Böhmová, Vlasta; Obalová, L.

    2012-01-01

    Roč. 179, č. 1 (2012), s. 164-169 ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/1762; GA ČR GD203/08/H032 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z30130516 Keywords : mixed oxide catalysts * voc oxidation * titania Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.980, year: 2012

  6. 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

  7. Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

    DEFF Research Database (Denmark)

    Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

    2011-01-01

    Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

  8. 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

  9. 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.

  10. Effect of drying method on properties of vanadium-molybdenum oxide catalysts

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Savchenko, L.A.; Tarasova, D.V.; Tret'yakov, Yu.D.; Olen'kova, I.P.; Nikoro, T.A.; Maksimov, N.G.

    1981-01-01

    Effect of drying method of molybdenum and vanadium salt solutions on physicochemical and catalytical properties of vanadium-molybdenum catalysts is studied. It is shown that the drying method of solutions determines the completeness of vanadium binding into oxide vanadium-molybdenum compounds and thus effects the activity and selectivity of catalysts in acrolein oxidation into acrylic acid. Besides the drying method determines the porous structure of catalysts [ru

  11. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun

    2016-01-22

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  12. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun; Shin, Chae-Ho

    2016-01-01

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  13. Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

    Energy Technology Data Exchange (ETDEWEB)

    Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

    2005-09-18

    A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

  14. Ni catalysts with different promoters supported on zeolite for dry reforming of methane

    KAUST Repository

    Alotaibi, Raja; Alenazey, Feraih; Alotaibi, Faisal; Wei, Nini; Al-Fatesh, Ahmed; Fakeeha, Anis

    2015-01-01

    Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

  15. Ni catalysts with different promoters supported on zeolite for dry reforming of methane

    KAUST Repository

    Alotaibi, Raja

    2015-07-08

    Dry reforming of methane (DRM) is considered a high endothermic reaction with operating temperatures between 700 and 1000 °C to achieve high equilibrium conversion of CH4 and CO2 to the syngas (H2 and CO). The conventional catalysts used for DRM are Ni-based catalysts. However, many of these catalysts suffer from the short longevity due to carbon deposition. This study aims to evaluate the effect of La and Ca as promoters for Ni-based catalysts supported on two different zeolite supports, ZL (A) (BET surface area = 925 m2/g, SiO2/Al2O3 mol ratio = 5.1), and ZL (B) (BET surface area = 730 m2/g, SiO2/Al2O3 mol ratio = 12), for DRM. The physicochemical properties of the prepared catalysts were characterized with XRD, BET, TEM and TGA. These catalysts were tested for DRM in a microtubular reactor at reaction conditions of 700 °C. The catalyst activity results show that the catalysts Ni/ZL (B) and Ca-Ni/ZL (B) give the highest methane conversion (60 %) with less time on stream stability compared with promoted Ni on ZL (A). In contrast, La-containing catalysts, La-Ni/ZL (B), show more time on stream stability with minimum carbon content for the spent catalyst indicating the enhancement of the promoters to the Ni/ZL (A) and (B), but with less catalytic activity performance in terms of methane and carbon dioxide conversions due to rapid catalyst deactivation.

  16. Fischer-Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions

    Energy Technology Data Exchange (ETDEWEB)

    A.R. de la Osa; A. De Lucas; A. Romero; J.L. Valverde; P. Sanchez [University of Castilla-La Mancha, Ciudad Real (Spain). Chemical Engineering Department

    2011-05-15

    The effects of reaction conditions on the Fischer-Tropsch activity and product distribution of an alkali-earth metal promoted cobalt based catalyst were studied. The influence of the promoter on the reducibility and cobalt particle size was studied by different techniques, including N{sub 2} adsorption, X-ray diffraction, temperature-programmed reduction, temperature-programmed desorption and acid-base titrations. Experiments were carried out on a bench-scale fixed bed reactor and catalysts were prepared by incipient wetness impregnation. It was observed that addition of a small amount of calcium oxide as a promoter (0.6 wt.%) improved the cobalt oxide reducibility and reduced the formation of cobalt-aluminate species. A positive correlation between basicity and particle size was observed. In terms of FTS results, CO conversion and C{sub 5}{sup +} selectivity were found to be enhanced by the addition of this promoter. It was important to note that the addition of calcium shifted the distribution to mainly C{sub 16}-C{sub 18} hydrocarbons fraction, which could be greatly considered for a diesel formulation. Furthermore, the variation of the reaction conditions seemed to influence product distribution in a lesser extent than unpromoted catalyst. Also, a displacement of hydrocarbon distribution to higher molecular weight with decreasing space velocity and temperature was observed. Moreover, the addition of calcium to the cobalt based catalyst was found to greatly maintain selectivity to C{sub 5}{sup +} for a wide range of H{sub 2}/CO molar ratios. 60 refs., 10 figs., 5 tabs.

  17. Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

    International Nuclear Information System (INIS)

    Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

    2014-01-01

    This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H 2 -temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H 2 /CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C 5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum

  18. Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

    Energy Technology Data Exchange (ETDEWEB)

    Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my [Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Ali, Sardar, E-mail: alikhan-635@yahoo.com [Centralized Analytical Laboratory, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my [Department of Chemical Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

    2014-10-24

    This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

  19. Stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1979-03-01

    The stepwise mechanism of oxidative ammonolysis of propane to acrylonitrile over gallium-antimony oxide catalysts GaSb/sub 19/O/sub x/, GaSb/sub 3/Ni/sub 1.5/0/sub x/, and GaSb/sub 2.5/Ni/sub 1.5/PW/sub 0//sub 0.25/O/sub x/ was studied at 450/sup 0/ and 550/sup 0/C by introducing alternating pulses of 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/helium (to reduce the steady-state catalytic surface) and 0.5Vertical Bar3< propane/0.6Vertical Bar3< ammonia/1.86Vertical Bar3< oxygen/helium mixtures into a fluidized-bed catalytic reactor. Over all the catalysts studied, the rates of acrylonitrile formation during the two types of pulses were very similar, but carbon dioxide was formed much faster during the reducing pulses, particularly at 450/sup 0/C. These findings suggested that acrylonitrile is formed by a stepwise redox mechanism involving consecutive interaction of propane and ammonia with the surface oxygen of the catalysts and oxidation of the reduced catalyst surface by gas-phase oxygen. The formation of carbon dioxide proceeds by both stepwise and associative mechanisms, the latter being more important at higher temperatures. The results are similar to published results for ammoxidation of propylene and olefins.

  20. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

    DEFF Research Database (Denmark)

    Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation...... of benzylic, alicyclic and unsaturated alcohols to their corresponding carbonyl compounds with excellent selectivities. The observed trend in activity for conversion of substituted alcohols suggested a β-H elimination step to be involved, thus enabling a possible reaction mechanism for oxidative...... dehydrogenation of benzyl alcohols to be proposed. The use of CuO as an inexpensive and efficient heterogeneous catalyst under aerobic conditions provides a new noble metal-free and green reaction protocol for carbonyl compound synthesis....

  1. Application of a mixed metal oxide catalyst to a metallic substrate

    Science.gov (United States)

    Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

    2009-01-01

    A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

  2. Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2011-07-01

    In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

  3. Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

    2013-11-01

    The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

  4. Poly (p-phenylendiamine/TiO2) nanocomposite promoted Pt/C catalyst for methanol and ethanol electrooxidation in alkaline medium

    International Nuclear Information System (INIS)

    Rostami, Hussein; Rostami, Abbas Ali; Omrani, Abdollah

    2016-01-01

    In the present study, poly (p-phenylendiamine/titanium dioxide) (PpPDA/TiO 2 ) nanocomposites (NCs) were prepared by in situ polymerization of p-phenylenediamine monomer with of different TiO 2 loading. A facile method was developed to promote the electrocatalytic activity of commercial Pt/C catalyst by ultrasonically mixing Pt/C catalyst and PpPDA/TiO 2 NCs. The PpPDA/TiO 2 NC, Pt/C catalyst and composite catalyst of Pt/C + PpPDA/TiO 2 were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. The surface morphology of Pt/C is significantly influenced by the presence of PpPDA/TiO 2 NC as confirmed by SEM observations. Cyclic voltammetry (CV) measurements showed that the PpPDA/TiO 2 NC leads to a significant improvement in the activity and stability of Pt/C for alcohol oxidation especially for ethanol oxidation in alkaline medium. For Pt/C + PpPDA/TiO 2 , the onset potentials shift to negative values by 30 and 160 mV compared to the onset potentials of Pt/C for methanol and ethanol oxidation, respectively. Chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) results also confirmed that this composite catalyst has superior catalytic performance towards ethanol oxidation compared to the pure Pt/C catalyst.

  5. NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

    Energy Technology Data Exchange (ETDEWEB)

    Craig E. Barnes

    2013-03-05

    A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

  6. On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

    KAUST Repository

    Quinet, Elodie

    2009-12-10

    The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

  7. On the mechanism of hydrogen-promoted gold-catalyzed CO oxidation

    KAUST Repository

    Quinet, Elodie; Piccolo, Laurent; Morfin, Franck; Avenier, Priscilla; Diehl, Fabrice; Caps, Valerie; Rousset, Jean Luc

    2009-01-01

    The kinetics of CO oxidation, H2 oxidation and preferential CO oxidation (PrOx) over Au/Al2O3 catalysts have been investigated. The catalysts with the smallest particles (∼2 nm) are the most active for all three reactions. As previously observed, the presence of H2 greatly promotes CO oxidation, which becomes faster than CO-free H2 oxidation at low temperature. From these results and on the basis of previous works, we propose a complete PrOx mechanism. The reaction involves Au-OOH, Au-OH and Au-H intermediates, also involved in H2 oxidation, and benefits from the presence of low-coordination sites. © 2009 Elsevier Inc. All rights reserved.

  8. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  9. Atomic origins of water-vapour-promoted alloy oxidation.

    Science.gov (United States)

    Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K; Baer, Donald R; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M; Xu, Zhijie; Wang, Chongmin

    2018-05-07

    The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion 1-4 . Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys 5,6 . However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

  10. Selectivities of rare earth oxide catalysts for dehydration of butanols

    International Nuclear Information System (INIS)

    Bernal, S.; Trillo, J.M.

    1980-01-01

    The catalytic dehydration of 2-propanol, 1-butanol, and 2-butanol over La 2 O 3 , CeO 2 , Pr 6 O 11 , Sm 2 O 3 , Eu 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , and Yb 2 O 3 is studied. Because of the gradual variation of the general properties of 4f oxides, the former group has been considered a likely series to analyze the existence of definite correlations between alkene distribution and catalyst properties, often reported in the literature. According to our study, the effect of temperature on product distribution may strongly restrict the validity of such correlations. This point is discussed on the basis of the linear relationships found here between the activation energy (E/sub a/) and the log of the preexponential factor

  11. Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Patel, B.M.; Price, G.L.

    1990-01-01

    This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with 18 O 2 have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C 3 D 6 reaction. No isotope effect is observed for carbon dioxide formation from C 3 D 6 suggesting that CO 2 is formed by parallel, not consecutive, oxidation of propylene

  12. 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.

  13. Catalytic Activity and Deactivation of SO2 Oxidation Catalysts in Simulated Power Plant Flue Gases

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Chrissanthopoulos, Asthanassios; Eriksen, Kim Michael

    1997-01-01

    The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas.......The catalyst deactivation and the simultaneious formation of compounds in commercial SO2 oxidation catalysts have been studied by combined activity measurements and in situ EPR spectroscopy in the temperature range 350-480 C in wet and dry simulated power plant flue gas....

  14. Influence of Reduction Promoters on Stability of Cobalt/g-Alumina Fischer-Tropsch Synthesis Catalysts

    OpenAIRE

    Gary Jacobs; Wenping Ma; Burtron H. Davis

    2014-01-01

    This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing...

  15. Promotion of Nb2O5 on the wustite-based iron catalyst for ammonia synthesis

    International Nuclear Information System (INIS)

    Han, Wenfeng; Huang, Shiliang; Cheng, Tianhong; Tang, Haodong; Li, Ying; Liu, Huazhang

    2015-01-01

    Highlights: • Niobium enhances the reduction of wustite-based ammonia synthesis catalyst significantly. • Nb 2 O 5 inhibits the segregation or formation of solid solutions on the catalyst surface. • Nb 2 O 5 doping enhances the growth rates of [2 1 1] and [2 0 0] planes rather than their amounts. - Abstract: Niobium was selected and investigated as a potential promoter for wustite-based catalyst (WBC) for ammonia synthesis. Experiments on reduction performance, activity test and H 2 -TGA, in situ XRD as well as XPS were carried out to obtain the promotion effect and mechanism involved. Niobium as a promoter was confirmed to enhance the reduction of WBC significantly. This behavior is highly desired for industry in terms of catalyst regeneration and lesser pretreatment time for fabrication regardless the unimproved catalytic performance for Nb 2 O 5 -doped wustite-based catalyst (Nb-WBC). Possible reasons for these phenomena are discussed. It is suggested that Nb 2 O 5 is not favorable for the segregation or formation of solid solutions on the catalyst surface, which are difficult to be reduced. However, it seems that niobium does not promote the growth of [2 1 1] plane, which is active for ammonia synthesis.

  16. Formation of nitrogen compounds from nitrogen-containing rings during oxidative regeneration of spent hydroprocessing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.; Nielsen, M.; Jurasek, P. [CANMET, Ottawa, ON (Canada). Energy Research Laboratories

    1995-05-01

    Commercial CoMo and NiMo catalysts in an oxidic and sulfided form and a {gamma}-alumina were deposited with pyrrole, pyridine, and quinoline. The deposited catalysts and two spent hydroprocessing catalysts were pyrolyzed and oxidized under conditions typical of regeneration of hydroprocessing catalysts. The formation of NH{sub 3} and HCN, as well as selected cases of N{sub 2}O and NO, was monitored during the experiments. NH{sub 3} and HCN were formed during pyrolysis of pyrrole-deposited catalysts whereas only NH{sub 3} was formed during that of pyridine-and quinoline-deposited catalysts. For all deposited catalysts, both NH{sub 3} and HCN were formed during temperature programmed oxidation in 2% O{sub 2}. For spent catalysts, a small amount of N{sub 2}O was formed in 2 and 4% O{sub 2}. For pyrrole-deposited catalysts, large yields of N{sub 2}O were formed in 4% O{sub 2}. Under the same conditions, N{sub 2}O yields for pyridine- and quinoline-deposited catalysts were very small. 13 refs., 12 figs., 6 tabs.

  17. Role of ultrasonic irradiation on transesterification of palm oil using calcium oxide as a solid base catalyst

    International Nuclear Information System (INIS)

    Poosumas, Jutipong; Ngaosuwan, Kanokwan; Quitain, Armando T.; Assabumrungrat, Suttichai

    2016-01-01

    Highlights: • Transesterification of palm oil using a circulated continuous flow ultrasonic reactor. • Heterogeneous system using CaO as catalyst. • Effects of ultrasonic frequency and power, and catalyst reusability were considered. • A single high frequency and high intensity irradiation is favorable for heterogeneous system. - Abstract: Biodiesel production from transesterification of palm oil using a circulated continuous flow ultrasonic reactor was investigated. Transesterification was carried out at 60 °C, 1 atm and a methanol-to-oil molar ratio of 9:1. The highest reaction rate was achieved at the catalyst loading of 2 wt%, and biodiesel yield constantly increased until transesterification equilibrium (about 80%) was reached. A higher ultrasonic frequency (50 kHz) promoted the heterogeneously catalyzed transesterification of refined palm oil, because the three-phase system (packed solid catalyst, methanol and oil) required more spatial distribution by ultrasonic irradiation. Moreover, the highest ultrasonic power also provided highest transesterification rate and biodiesel yield due to cavitation activity enhancement. Reusability of calcium oxide catalysts was also investigated, and results showed that this can be reused to provide high biodiesel yield for at least three operations with slight decrease in the rate of reaction due to counter balance effect of organic compounds deposition on the catalyst surface. The results from this study can be a basis for scaling up of the process to industrial scale.

  18. Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas.

    Science.gov (United States)

    Yang, Jianping; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

    2014-12-16

    To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.

  19. Iridium Sulfide and Ir Promoted Mo Based Catalysts.

    Czech Academy of Sciences Publication Activity Database

    Vít, Zdeněk

    2007-01-01

    Roč. 322, - (2007), s. 142-151 ISSN 0926-860X R&D Projects: GA ČR(CZ) GA104/06/0870 Institutional research plan: CEZ:AV0Z40720504 Keywords : iridium sulfide * IrMo catalyst * hydrodesulfurization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.166, year: 2007

  20. Effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts

    International Nuclear Information System (INIS)

    Satsuma, Atsushi; Maeshima, Hajime; Watanabe, Kiyoshi; Hattori, Tadashi

    2001-01-01

    The inhibitory effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts was investigated. The activity of nitrous oxide decomposition significantly decreased over CuO, Co 3 O 4 , NiO, Fe 2 O 3 , SnO 2 , In 2 O 3 and Cr 2 O 3 by reversible adsorption of oxygen onto the active sites. On the contrary to this, there was no or small change in the activity of TiO 2 , Al 2 O 3 , MgO, La 2 O 3 and CaO. A good correlation was observed between the degree of inhibition and the heat of formation of metal oxides. On the basis of kinetic model, the reduction of catalytic activity in the presence of oxygen was rationalized with the strength of oxygen adsorption on the metal oxide surface. (author)

  1. Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

    KAUST Repository

    Zwaschka, Gregor; Rondelli, Manuel; Krause, Maximilian; Rö tzer, Marian David; Hedhili, Mohamed N.; Heiz, Ulrich; Basset, Jean-Marie; Schweinberger, Florian; D'Elia, Valerio

    2018-01-01

    The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

  2. Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

    KAUST Repository

    Zwaschka, Gregor

    2018-01-22

    The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

  3. 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.

  4. ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES/CLEAN DIESEL TECHNOLOGIES FUEL BORNE CATALYST WITH CLEANAIR SYSTEM'S DIESEL OXIDATION CATALYST

    Science.gov (United States)

    The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with CleanAir System's Diesel Oxidation Catalyst manufactured by Clean Diesel Technologies, Inc. The technology is a fuel-borne catalyst used in ultra low sulfur d...

  5. SSZ-13-supported manganese oxide catalysts for low temperature ...

    Indian Academy of Sciences (India)

    YONGZHOU YE

    Their performances for the selective catalytic reduction (SCR) of NOx with NH3 were evaluated. ... catalysts have received considerable attention.2,3 More- over, catalysts ..... zeolite channels or causing agglomeration on the cat- alyst surface ...

  6. Preparation and Characterization of Promoted Fe-V/SiO2 Nanocatalysts for Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Hamid Reza Rafiee

    2013-01-01

    Full Text Available A series of SiO2 supported iron-vanadium catalysts were prepared using sol-gel and wetness impregnation methods. This research investigates the effects of V and Cu on the structure and morphology of Fe/SiO2 catalysts. The SiO2 supported catalyst with the highest specific surface area and pore volume was obtained when it is containing 40 wt.% Fe, 15 wt.% V, and 2 wt.% Cu. Characterization of prepared catalysts was carried out by powder X-ray diffraction (XRD, scanning electron microcopy (SEM, vibrating sample magnetometry (VSM, Fourier transform infrared (FT-IR spectrometry, temperature program reduction (TPR, N2 physisorption, and thermal analysis methods such as thermal gravimetric analysis (TGA and differential scanning calorimetry (DSC. The Fe-V/SiO2 catalyst promoted with 2 wt.% of Cu exhibited typical ferromagnetic behavior at room temperature with a saturation magnetization value of 11.44 emu/g. This character of catalyst indicated great potential for application in magnetic separation technologies. The prepared catalyst was found to act as an efficient recoverable nanocatalyst for oxidation reaction of alcohols to aldehydes and ketones in aqueous media under mild condition. Moreover, the catalyst was reused five times without significant degradation in catalytic activity and performance.

  7. Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

    NARCIS (Netherlands)

    van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

    1999-01-01

    The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

  8. Phenol oxidation by a sequential CWPO-CWAO treatment with a Fe/AC catalyst.

    Science.gov (United States)

    Quintanilla, A; Fraile, A F; Casas, J A; Rodríguez, J J

    2007-07-31

    Catalytic wet peroxide oxidation (CWPO) of phenol with a homemade Fe/activated carbon (Fe/AC) catalyst has been studied in a stainless steel fixed-bed reactor at different operating conditions (T=23-100 degrees C, P(T)=1-8atm, W=0-2.5g, and tau=20-320g(CAT)h/g(Phenol)). The results show that, thanks to the incorporation of Fe on the activated carbon, phenol conversion improved dramatically, reaching a 90% at 65 degrees C, 2atm, and 40g(CAT)h/g(Phenol). However, TOC conversion values remain fairly low, (around 5% at 40g(CAT)h/g(Phenol)), and no improvement was obtained with the inclusion of Fe. The presence of Fe seems to promote the nondesirable coupling reactions that take place in CWPO of phenol due to the condensation of the ring intermediates (the primary phenol oxidation products). These condensation products are quite refractory to CWPO at the conditions employed. Taking advantage of the high phenol conversions in CWPO and the high phenol mineralization in CWAO, along with the good stability of the Fe/AC catalyst, a CWPO-CWAO sequential treatment has been successfully performed by using a fixed-bed and trickle-bed reactor in series. A CWPO treatment at ambient conditions followed by a CWAO treatment at mild conditions (100 degrees C and 8atm) is presented as high efficiency process for the decontamination of phenolic wastewaters.

  9. Phenol oxidation by a sequential CWPO-CWAO treatment with a Fe/AC catalyst

    International Nuclear Information System (INIS)

    Quintanilla, A.; Fraile, A.F.; Casas, J.A.; Rodriguez, J.J.

    2007-01-01

    Catalytic wet peroxide oxidation (CWPO) of phenol with a homemade Fe/activated carbon (Fe/AC) catalyst has been studied in a stainless steel fixed-bed reactor at different operating conditions (T = 23-100 deg. C, P T = 1-8 atm, W = 0-2.5 g, and τ = 20-320 g CAT h/g Phenol ). The results show that, thanks to the incorporation of Fe on the activated carbon, phenol conversion improved dramatically, reaching a 90% at 65 deg. C, 2 atm, and 40 g CAT h/g Phenol . However, TOC conversion values remain fairly low, (around 5% at 40 g CAT h/g Phenol ), and no improvement was obtained with the inclusion of Fe. The presence of Fe seems to promote the nondesirable coupling reactions that take place in CWPO of phenol due to the condensation of the ring intermediates (the primary phenol oxidation products). These condensation products are quite refractory to CWPO at the conditions employed. Taking advantage of the high phenol conversions in CWPO and the high phenol mineralization in CWAO, along with the good stability of the Fe/AC catalyst, a CWPO-CWAO sequential treatment has been successfully performed by using a fixed-bed and trickle-bed reactor in series. A CWPO treatment at ambient conditions followed by a CWAO treatment at mild conditions (100 deg. C and 8 atm) is presented as high efficiency process for the decontamination of phenolic wastewaters

  10. Studies on mixed metal oxides solid solutions as heterogeneous catalysts

    Directory of Open Access Journals (Sweden)

    H. R. Arandiyan

    2009-03-01

    Full Text Available In this work, a series of perovskite-type mixed oxide LaMo xV1-xO3+δ powder catalysts (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0, with 0.5 < δ < 1.5, prepared by the sol-gel process and calcined at 750ºC, provide an attractive and effective alternative means of synthesizing materials with better control of morphology. Structures of resins obtained during the gel formation process by FT-IR spectroscopy and XRD analysis showed that all the LaMo xV1-xO3+δ samples are single phase perovskite-type solid solutions. The surface area (BET between 2.5 - 5.0 m²/g (x = 0.1 and 1.0 respectively increases with increasing Mo ratio in the samples. They show high purity, good chemical homogeneity, and lower calcinations temperatures as compared with the solid-state chemistry route. SEM coupled to EDS and thermogravimetric analysis/differential thermal analyses (TGA/DTA have been carried out in order to evaluate the homogeneity of the catalyst. Finally, the experimental studies show that the calcination temperature and Mo content exhibited a significant influence on catalytic activity. Among the LaMo xV1-xO3+δ samples, LaMo0.7V0.3O4.2 showed the best catalytic activity for the topic reaction and the best activity and stability for ethane reforming at 850ºC under 8 bar.

  11. Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2011-07-01

    Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

  12. Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

    Science.gov (United States)

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-02-29

    Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO(x)/ZrO2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WOx/ZrO2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO2) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO3 and monoclinic ZrO2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WOx/ZrO2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. STUDY OF EPOXIDE DECYCLISATION OF CARYOPHYLENE OXIDE WITH SYNTHETIC ZEOLITE AS CATALYSTS

    Directory of Open Access Journals (Sweden)

    Winarto Haryadi

    2010-06-01

    Full Text Available The reaction of epoxide ring opening of caryophillene oxide has been done using zeolite H-Y, H-sodalit, and H-ZSM-5 as catalysts. The reactions were done in two types, there were in dioxane solvent at temperature of 110 oC and without solvent at temperature of 175 oC. The catalyst weight was 10 % from caryophillene oxide weight, and the time of reaction was four hours. The product of reaction was analyzed using GC, FTIR, and GC-MS. The reactions of caryophillene oxide in dioxane solvent with the three kinds of zeolites did not give any targeted product. Whereas, the reactions without solvent gave three main products, there was one compound with one group of secondary hidroxyl (secondary alcohol, and two compounds of ketone from caryophillene. The reaction product of caryophillene oxide obtained without using solvent with the three type of catalysts were then compared. Conversion of three main products produced by H-ZSM-5 catalyst, H-sodalit catalyst and H-Y catalyst were 82.11 %, 54.92 % and 38.53 % respectively. For that reason, the transformation of caryophillene oxide using H-ZSM-5 catalyst was considered to be the best selective product. The alcohol product was resulted from reaction between caryophillene oxide and Bronsted acid, and  the ketone products was resulted from the reaction with Lewis acid in zeolite.   Keywords: Epoxide ring opening, HY, H-sodalit and HZSM-5

  14. Effect of coke and catalyst structure on oxidative regeneration of hydroprocessing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E. (CANMET, Ottawa, ON (Canada). Energy Research Laboratories)

    1991-04-01

    Two industrial hydroprocessing catalysts used for upgrading an atmospheric residue and a gas oil, respectively were regenerated in a fixed bed using air and 2 vol.% O{sub 2}+N{sub 2} balance mixture. The regeneration in air resulted in a significant sintering of the catalyst's material. The surface area of catalysts regenerated in 2 vol.% O{sub 2} mixture was similar to that of fresh catalysts, whereas a significant loss of surface area was observed after regeneration in air. The X-ray diffraction pattern of catalysts regenerated in 2 vol.% O{sub 2}+N{sub 2} balance mixture was also similar to that of fresh catalysts. 22 refs., 9 figs., 7 tabs.

  15. Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts

    Directory of Open Access Journals (Sweden)

    R. Prasad

    2011-05-01

    Full Text Available CuO-CeO2 systems have been proposed as a promising catalyst for low temperature diesel-soot oxidation. CuO-CeO2 catalysts prepared by various methods were examined for air oxidation of the soot in a semi batch tubular flow reactor. The air oxidation of soot was carried out under tight contact with soot/catalyst ratio of 1/10. Air flow rate was 150 ml/min, soot-catalyst mixture was 110 mg, heating rate was 5 0C/min. Prepared catalysts were calcined at 500 0C and their stability was examined by further heating to 800 0C for 4 hours. It was found that the selectivity of all the catalysts was nearly 100% to CO2 production. It was observed that the activity and stability of the catalysts greatly influenced by the preparation methods. The strong interaction between CuO and CeO2 is closely related to the preparation route that plays a crucial role in the soot oxidation over the CuO-CeO2 catalysts. The ranking order of the preparation methods of the catalysts in the soot oxidation performance is as follows: sol-gel > urea nitrate combustion > Urea gelation method > thermal decomposition > co-precipitation. Copyright © 2011 BCREC UNDIP. All rights reserved.(Received: 27th June 2010, Revised: 7th August 2010; Accepted: 13rd October 2010[How to Cite: R. Prasad, V.R. Bella. (2011. Comparison of Preparation Methods of Copper Based PGMFree Diesel-Soot Oxidation Catalysts. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 15-21. doi:10.9767/bcrec.6.1.822.15-21][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.822.15-21 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/822 | View in 

  16. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    Science.gov (United States)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

  17. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...

  18. Polyethers for biomedical applications. Polymerization of propylene oxide by organozinc/organotin catalysts

    NARCIS (Netherlands)

    Bots, Jan Gert; van der Does, L.; Bantjes, Adriaan; Broersma, Jaap

    1987-01-01

    The polymerization of propylene oxide to obtain a high-molecular-weight polymer with an atactic structure required for the application as artificial blood vessels was investigated using combinations of organozinc and organotin compounds as catalyst. The composition of the most active catalyst,

  19. Physico-Chemical and Structural Properties of DeNOx and SO2 Oxidation Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen Grenville; Oehlers, Cord; Nielsen, Kurt

    1996-01-01

    Commercial catalysts for NOx removal and SO2 oxidation and their model systems have been investigated by spectroscopic, thermal, electrochemical and X-ray methods. Structural information on the vanadium complexes and compounds as well as physico-chemical properties for catalyst model systems have...

  20. Complex catalysts from self-repairing ensembles to highly reactive air-based oxidation systems

    Science.gov (United States)

    Craig L. Hill; Laurent Delannoy; Dean C. Duncan; Ira A. Weinstock; Roman F. Renneke; Richard S. Reiner; Rajai H. Atalla; Jong Woo Han; Daniel A. Hillesheim; Rui Cao; Travis M. Anderson; Nelya M. Okun; Djamaladdin G. Musaev; Yurii V. Geletii

    2007-01-01

    Progress in four interrelated catalysis research efforts in our laboratory are summarized: (1) catalytic photochemical functionalization of unactivated CeH bonds by polyoxometalates (POMs); (2) self-repairing catalysts; (3) catalysts for air-based oxidations under ambient conditions; and (4) terminal oxo complexes of the late-transition metal elements and their...

  1. Aerobic Oxidation of 5-(Hydroxymethyl)furfural in Ionic Liquids with Solid Ruthenium Hydroxide Catalysts

    DEFF Research Database (Denmark)

    Ståhlberg, Tim Johannes Bjarki; Eyjolfsdottir, Ester; Gorbanev, Yury

    2012-01-01

    The aerobic oxidation of 5-(hydroxymethyl)furfural was investigated over solid ruthenium hydroxide catalysts in ionic liquids at elevated temperatures and pressures. Several different catalyst supports were tested in combination with various ionic liquids. The best result was obtained in [EMIm...

  2. Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

    1984-01-01

    The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

  3. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Sangaru, Shiv; Saih, Youssef; Ould-Chikh, Samy; Basset, Jean-Marie

    2015-01-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta

  4. Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

    NARCIS (Netherlands)

    Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

    1982-01-01

    Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

  5. Oxidation of elemental mercury by modified spent TiO2-based SCR-DeNOx catalysts in simulated coal-fired flue gas.

    Science.gov (United States)

    Zhao, Lingkui; Li, Caiting; Zhang, Xunan; Zeng, Guangming; Zhang, Jie; Xie, Yin'e

    2016-01-01

    In order to reduce the costs, the recycle of spent TiO2-based SCR-DeNOx catalysts were employed as a potential catalytic support material for elemental mercury (Hg(0)) oxidation in simulated coal-fired flue gas. The catalytic mechanism for simultaneous removal of Hg(0) and NO was also investigated. The catalysts were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) method. Results indicated that spent TiO2-based SCR-DeNOx catalyst supported Ce-Mn mixed oxides catalyst (CeMn/SCR1) was highly active for Hg(0) oxidation at low temperatures. The Ce1.00Mn/SCR1 performed the best catalytic activities, and approximately 92.80% mercury oxidation efficiency was obtained at 150 °C. The inhibition effect of NH3 on Hg(0) oxidation was confirmed in that NH3 consumed the surface oxygen. Moreover, H2O inhibited Hg(0) oxidation while SO2 had a promotional effect with the aid of O2. The XPS results illustrated that the surface oxygen was responsible for Hg(0) oxidation and NO conversion. Besides, the Hg(0) oxidation and NO conversion were thought to be aided by synergistic effect between the manganese and cerium oxides.

  6. METHANOL OXIDATION OVER AU/ γ -AL 2O3 CATALYSTS 149

    African Journals Online (AJOL)

    DR. AMINU

    catalysts were used to catalyze the oxidation of methanol and characterised using X-ray ... As the concentration of methoxy diminishes, so the mechanism reverts to a decomposition pathway ..... Catalysis Reviews: Science and Engineering 41.

  7. Oxidation Catalysts for Elemental Mercury in Flue Gases—A Review

    Directory of Open Access Journals (Sweden)

    Liliana Lazar

    2012-02-01

    Full Text Available The removal of mercury from flue gases in scrubbers is greatly facilitated if the mercury is present as water-soluble oxidized species. Therefore, increased mercury oxidation upstream of scrubber devices will improve overall mercury removal. For this purpose heterogeneous catalysts have recently attracted a great deal of interest. Selective catalytic reduction (SCR, noble metal and transition metal oxide based catalysts have been investigated at both the laboratory and plant scale with this objective. A review article published in 2006 covers the progress in the elemental mercury (Hgel catalytic oxidation area. This paper brings the review in this area up to date. To this end, 110 papers including several reports and patents are reviewed. For each type of catalyst the possible mechanisms as well as the effect of flue gas components on activity and stability are examined. Advantages and main problems are analyzed. The possible future directions of catalyst development in this environmental research area are outlined.

  8. Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

    KAUST Repository

    de Ruiter, J. M.; Purchase, R. L.; Monti, A.; van der Ham, C. J. M.; Gullo, M. P.; Joya, K. S.; D'Angelantonio, M.; Barbieri, A.; Hetterscheid, D. G. H.; de Groot, H. J. M.; Buda, F.

    2016-01-01

    derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques, and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst

  9. Chlorination of antimony and its volatilization treatment of waste antimony-uranium composite oxide catalyst

    International Nuclear Information System (INIS)

    Sawada, K.; Enokida, Y.

    2011-01-01

    For the waste antimony-uranium composite oxide catalyst, the chlorination of antimony and its volatilization treatment were proposed, and evaluated using hydrogen chloride gas at 873-1173 K. During the treatment, the weight loss of the composite oxide sample, which resulted from the volatilization of antimony, was confirmed. An X-ray diffraction analysis showed that uranium oxide, U 3 O 8 , was formed during the reaction. After the treatment at 1173 K for 1 h, almost all the uranium contained in the waste catalyst was dissolved by a 3 M nitric acid solution at 353 K within 10 min, although that of the non-treated catalyst was less than 0.1%. It was found that the chlorination and volatilization treatment was effective to separate antimony from the composite oxide catalyst and change uranium into its removable form. (orig.)

  10. Effect of Ca, Ce or K oxide addition on the activity of Ni/SiO{sub 2} catalysts for the methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Beatriz; Torres-Garcia, Enelio [Instituto Mexicano del Petroleo, Programa de Procesos y Reactores, Eje C. 152, Mexico, D.F., C.P. 07730 (Mexico); Valenzuela, Miguel A.; Palacios, Jorge [Instituto Politecnico Nacional-ESIQIE, Lab. Catalisis y Materiales, Zacatenco, Mexico, D.F., C.P. 07738 (Mexico)

    2010-11-15

    To increase the activity and stability of Ni/SiO{sub 2} catalysts, a series of Ni-Ca, Ni-K and Ni-Ce promoted catalysts were prepared by successive impregnations. The textural properties, reducibility and catalytic performance in the methane decomposition reaction were investigated. The catalyst containing 30 wt.% Ni and 30 wt.% cerium oxide greatly increased the conversion of methane (90% of equilibrium value) and improved the stability, whereas the Ni-K and Ni-Ca were less active and stable than the Ni/SiO{sub 2} catalyst. The results suggest that Ce addition prevents the sintering of nickel particles during reduction process maintaining a random distribution between the silica and cerium oxide improving the distribution and migration of deposited carbon. (author)

  11. Role of CeO2 promoter in NiO/α-Al2O3 catalyst for dry reforming of methane

    Science.gov (United States)

    Loc, Luu Cam; Phuong, Phan Hong; Tri, Nguyen

    2017-09-01

    A series of Ni/α-Al2O3 (NiAl) catalysts promoted by CeO2 was prepared by co-impregnation methods with content of (NiO+CeO2) being in the range of 10-30 wt%. The NiO:CeO2 weight ratio was fluctuated at 1:1, 1:2 and 1:3. Several techniques, including X-ray powder diffraction (XRD), Hydrogen temperature-programmed reduction (H2-TPR), and transmission electron microscopy (TEM) were used to investigate catalysts' physico-chemical properties. The activity of these catalysts in dry reforming of CH4 was investigated at temperature range of 550-800 °C. The results revealed that the most suitable CeO2 promoted Ni catalyst contained 20 wt% of (NiO+CeO2) and NiO:CeO2 weight ratio of 1:2. The best catalytic performance of catalyst [20(1Ni2Ce)Al] due to a better reducibility resulted in a higher amount of free small particle NiO. At 700 °C and CH4:CO2 molar ratio of 1:1, the conversion of CH4 and CO2 on the most suitable CeO2 promoted Ni catalyst reached 86% and 67%, respectively; H2 and CO selectivity of 90% and H2:CO molar ratio of 1.15 were obtained. Being similar to MgO [1], promoter CeO2 could improve catalytic activity of Ni/α-Al2O3 catalyst at a lower range of temperature. Besides, both MgO and CeO2 had a great impact on improving coke resistance of Ni catalysts. At higher temperature, the role of CeO2 as well as MgO in preventing coke formation on catalyst was clarified by temperature-programmed oxidation (TPO) technique. Coke amount formed after 30-h TOS on 20(1Ni2Ce) catalyst was found to be 22.18 mgC/gcat, being less than on non-promoted catalyst (36.75 mgC/gcat), but more than on 20(1Ni2Mg)Al one (5.25 mgC/gcat).

  12. Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

    International Nuclear Information System (INIS)

    Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

    2015-01-01

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO x /MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO x addition. • Bi-functional mechanism is facilitated in presence of CoO x . - Abstract: The electro-catalytic behavior of Pt-CoO x /MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH 4  as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO x , Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO ads on Pt active sites by the participation of CoO x . Compared to Pt/MWCNTs, Pt-CoO x /MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO x /MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups

  13. 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.

  14. 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.

  15. Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

    Science.gov (United States)

    Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

    2008-08-01

    The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

  16. Hydrogen purification for fuel cells using gold catalysts promoted with copper; Purificacao de hidrogenio para celulas a combustivel utilizando catalisadores de ouro promovidos com cobre

    Energy Technology Data Exchange (ETDEWEB)

    Mozer, Thiago Simonato; Passos, Fabio Barboza [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Engenharia Quimica e de Petroleo. Lab. de Reatores, Cinetica e Catalise (RECAT)]. E-mail: mozer@vm.uff.br

    2008-07-01

    The selective CO oxidation in the presence of H2 was investigated on Au catalysts promoted with different amounts of Cu. Au catalysts were prepared by the deposition-precipitation method and exhibited a satisfactory activity at 50 deg C with adequate selectivity. The addition of Cu to Au/Al{sub 2}O{sub 3} catalysts caused an increase in the selectivity to CO oxidation due to an interaction between Au and Cu on the surface of the catalysts. However, this beneficial effect was limited to an optimal content of Cu. Through the temperature programmed reduction (TPR) and ultraviolet visible diffuse reflectance spectroscopy (UV-vis DRS) techniques, the formation of small bimetallic Au-Cu particles was verified. The best result was obtained with 2.5% Au-0.5% Cu/Al{sub 2}O{sub 3} catalyst, the CO conversion was higher than 95% and the selectivity was around 70% at 50 deg C. The catalysts showed stable catalytic activity during 24 hours time -on-stream. In the presence of H{sub 2}O and CO{sub 2}, a small decrease in the CO conversion was observed in the stability test, probably due to the deactivation caused by the CO{sub 2} presence. (author)

  17. The effect of promoters on the electronic structure of ruthenium catalysts supported on carbon

    International Nuclear Information System (INIS)

    Guraya, Monica; Sprenger, Susanne; Rarog-Pilecka, Wioletta; Szmigiel, Dariusz; Kowalczyk, Zbigniew; Muhler, Martin

    2004-01-01

    Alkali- and earth-alkali-promoted ruthenium catalysts supported on graphitized carbon were investigated by means of X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) in order to study the effect of promoters on the electronic structure of this metal-support system. Samples were measured as prepared and after thorough reduction in hydrogen. The C 1s spectra of reduced alkali-promoted catalysts showed a shift towards higher binding energies and an asymmetric broadening. Neither non-promoted nor Ba-promoted Ru/C samples exhibited such a behaviour after similar treatments. The most important feature in the UP spectra of the reduced alkali-promoted catalysts was the appearance of a well defined Fermi edge absent in the semimetal-like electronic structure of graphite. No significant effects appeared in the case of non-promoted or Ba-promoted catalysts. The increase in the density of occupied states at the Fermi energy indicates a shift of this level into the conduction band, due to a charge transfer from the promoter to the support. This interpretation also provides an explanation for the observed higher C 1s binding energy and asymmetric broadening, due to the off-set introduced in the binding energy scale and the increasing probability of inelastic excitations near the Fermi level. In addition to photoelectron spectroscopy, low energy ion scattering (ISS) was used to obtain information about the localisation of the promoters. Based on the mild sputtering effect during prolonged series of spectra, it was possible to conclude that potassium covers both the carbon support and the Ru metal particles

  18. Biodiesel production using calcium manganese oxide as catalyst and different raw materials

    International Nuclear Information System (INIS)

    Dias, Joana Maia; Conceição Machado Alvim-Ferraz, Maria; Fonseca Almeida, Manuel; Méndez Díaz, José Diego; Sánchez Polo, Manuel; Rivera Utrilla, José

    2013-01-01

    Highlights: ► Biodiesel production using a calcium manganese oxide catalyst was studied. ► The active specie was Ca 0.9 Mn 0.1 O and its deactivation occurred by hydration. ► The studied catalyst presented lower activation temperature than CaO. ► Biodiesel production and quality using different raw materials is reported. ► Compared to the conventional process, biodiesel water content improved. - Abstract: The use of heterogeneous catalysts for biodiesel production aims to simplify the production process as well as to reduce purification costs and related environmental impacts. Calcium manganese oxide was recently identified by the authors as an interesting heterogeneous catalyst for biodiesel production from animal fat; however, the difference between this and other catalysts, the catalyst activation/deactivation mechanisms, its behaviour in the synthesis using different raw materials as well as the impacts of its use on product quality remained unclear. Therefore, the present work: (i) compared biodiesel production using calcium manganese oxide and other catalysts (CaO and NaOH); (ii) studied the reasons leading to activation/deactivation of the heterogeneous catalyst; (iii) analysed biodiesel heterogeneous synthesis using calcium manganese oxide and different raw materials (lard, waste frying oil and a mixture); and (iv) evaluated raw material and catalyst impact on the product quality. Considering the use of different catalysts, the results showed that, after 8 h of reaction, product purity was similar using the different catalysts, being 92.5 wt.% using both NaOH and calcium manganese oxide and 93.8 wt.% using CaO. The active species of the heterogeneous catalysts were CaO, in the case of calcinated calcium carbonate, and Ca 0.9 Mn 0.1 O, in the case of calcinated calcium manganese oxide. Because the deactivating species were different for both catalysts, the calcium manganese oxide required lower activation temperature, which should be an advantage

  19. Crystalline structure and propylene oxidation in complex bismuth-molybdenum oxide catalysts

    International Nuclear Information System (INIS)

    Manaila, R.; Ionescu, N.I.; Caldararu, M.

    1980-01-01

    Complex Bi-Mo oxide catalysts supported on amorphous SiO 2 were prepared by coprecipitation and tested in the reaction of selective oxidation of propylene to acrolein. They consist of a mixture of molybdate phases and excess MoO 3 . The Fe 2 (MoO 4 ) 3 phase was found to have a high concentration of lattice defects, induced by a Mo excess. These defects could be related to the catalytic conversion and to the selectivity to total oxidation by varying the calcination temperature. Calcination above 500 0 C induced also the transition of the metastable modification β-NiMoO 4 to the stable form α, accompanied by a loss of conversion. A complex Bi molybdate with scheelitic structure was found to have a high selectivity to acrolein. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-01-01

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

  1. 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.

  2. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    OpenAIRE

    Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell

    2009-01-01

    The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

  3. Cobalt oxide-based catalysts deposited by cold plasma for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kazimierski, P.; Jozwiak, L.; Sielski, J.; Tyczkowski, J., E-mail: jacek.tyczkowski@p.lodz.pl

    2015-11-02

    In proton exchange membrane fuel cells (PEMFC), both the anodic hydrogen oxidation reaction and the cathodic oxygen reduction reaction (ORR) require appropriate catalysts. So far, platinum-based catalysts are still the best option for this purpose. However, because these catalysts are too expensive for making commercially viable fuel cells, extensive research over the past decade has focused on developing noble metal-free alternative catalysts. In this paper, an approach based on cobalt oxide films fabricated by plasma-enhanced metal-organic chemical vapor deposition is presented. Such a material can be used to prepare catalysts for ORR in PEMFC. The films containing CoO{sub X} were deposited on a carbon paper thereby forming the electrode. Morphology and atomic composition of the films were investigated by scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively. The possibility of their application as the electro-catalyst for ORR in PEMFC was investigated and the electro-catalytic activities were evaluated by the electrochemical measurements and single cell tests. It was found that the fuel cell with Pt as the anode catalyst and CoO{sub X} deposit as the cathode catalyst was characterized by the open circuit voltage of 635 mV, Tafel slope of approx. 130 mV/dec and the maximum power density of 5.3 W/m{sup 2}. - Highlights: • Cobalt oxide catalyst for proton exchange membrane fuel cells was plasma deposited. • The catalyst exhibits activity for the oxygen reduction reaction. • Morphology and atomic composition of the catalyst were determined.

  4. Zeolite ZSM5 catalysts for abatement of nitrogen oxide

    Energy Technology Data Exchange (ETDEWEB)

    Ganemi, Bager

    1999-07-01

    Airborne pollutants from the combustion of fossil fuels are a global problem. Emission of nitrogen oxides (NO{sub x}) is increasing with the worldwide increase in the use of energy. Atmospheric and photochemical reactions link nitrogen oxides to hydrocarbons and tropospheric ozone. The emission of NO{sub x} has to be tackled urgently in order to limit the harmful effects of anthropogenic activity on the environment. The subject of this thesis is catalytic nitrogen oxide abatement through direct decomposition and reduction by methane over ion-exchanged zeolite ZSM5. The work covers catalytic conversion and surface intermediates, including correlations with the level of exchanged Cu{sup 2+} cations and Ni{sup 2+} or Pd{sup 2+} co-cations. Special attention is given to the aluminium content of the support and changes in structural parameters. It was found that NO{sub x} conversion over cation-exchanged ZSM5 is strongly influenced by the ion-exchange procedure and by the above material parameters. Characterization of Cu-ZSM5 reveals that approximately two molecules of water per Cu{sup 2+} ion desorb at temperatures between 150 and 350 Deg C, in addition to the conventional dehydration at lower temperatures. The desorbed water comes from the decomposition of Cu(OH){sub 2}. Decomposition of hydroxylated copper ions results in the formation Of Cu{sup 2+}-O-Cu{sup 2+} dimers, which are suggested to be the active sites for catalytic decomposition of NO. Acid sites are important for the dispersion of copper ions on the catalyst surface. Acid sites are also important for the interaction between copper species and the zeolite. Increased acidity leads to a stronger interaction between the exchanged cation and the framework, i.e. the exchanged cations become more resistant to mobility. The stronger bond between the exchanged cations and lattice oxygen also prevents dealumination of the catalyst and decreases the thermal expansion at higher temperatures. The temperature of

  5. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    Science.gov (United States)

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution.

    Science.gov (United States)

    Hung, Chang-Mao

    2009-07-30

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h(-1).

  7. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-30

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h{sup -1}.

  8. Activity of Cu-activated carbon fiber catalyst in wet oxidation of ammonia solution

    International Nuclear Information System (INIS)

    Hung, Chang-Mao

    2009-01-01

    Aqueous solutions of 200-1000 mg/L of ammonia were oxidized in a trickle-bed reactor using Cu-activated carbon fiber (ACF) catalysts, which were prepared by incipient wet impregnation with aqueous solutions of copper nitrate that was deposited on ACF substrates. The results reveal that the conversion of ammonia by wet oxidation in the presence of Cu-ACF catalysts was a function of the metal loading weight ratio of the catalyst. The total conversion efficiency of ammonia was 95% during wet oxidation over the catalyst at 463 K at an oxygen partial pressure of 3.0 MPa. Moreover, the effect of the initial concentration of ammonia and the reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid space velocity of less than 3.0 h -1 .

  9. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  10. A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

    Science.gov (United States)

    Hoover, Jessica M.; Stahl, Shannon S.

    2011-01-01

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  11. Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.

    Science.gov (United States)

    Yamazaki, Shin-ichi; Yamada, Yusuke; Takeda, Sahori; Goto, Midori; Ioroi, Tsutomu; Siroma, Zyun; Yasuda, Kazuaki

    2010-08-21

    Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.

  12. W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

    Science.gov (United States)

    Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

    2017-11-01

    W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

  13. 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

  14. The Effect of Annealing Temperature on Nickel on Reduced Graphene Oxide Catalysts on Urea Electrooxidation

    International Nuclear Information System (INIS)

    Glass, Dean E.; Galvan, Vicente; Prakash, G.K. Surya

    2017-01-01

    Highlights: •Nickel was reduced on graphene oxide and annealed under argon from 300 to 700 °C. •Nickel was oxidized from the removal of oxygen groups on the graphene oxide. •Higher annealed catalysts displayed decreased urea electrooxidation currents. •Micro direct urea/hydrogen peroxide fuel cells were employed for the first time. •Ni/rGO catalysts displayed enhanced fuel cell performance than the bare nickel. -- Abstract: The annealing temperature effects on nickel on reduced graphene oxide (Ni/rGO) catalysts for urea electrooxidation were investigated. Nickel chloride was directly reduced in an aqueous solution of graphene oxide (GO) followed by annealing under argon at 300, 400, 500, 600, and 700 °C, respectively. X-ray Diffraction (XRD) patterns revealed an increase in the crystallite size of the nickel nanoparticles while the Raman spectra displayed an increase in the graphitic disorder of the reduced graphene oxide at higher annealing temperatures due to the removal of oxygen functional groups. The Ni/rGO catalysts annealed at higher temperatures displayed oxidized nickel surface characteristics from the Ni 2p X-ray Photoelectron Spectra (XPS) due to the oxidation of the nickel from the oxygen functional groups in the graphitic lattice. In the half-cell testing, the onset potential of urea electrooxidation decreased while the urea electrooxidation currents decreased as the annealing temperature was increased. The nickel catalyst annealed at 700 °C displayed a 31% decrease in peak power density while the catalyst annealed at 300 °C displayed a 13% increase compared with the unannealed Ni/rGO catalyst in the micro direct urea/hydrogen peroxide fuel cells tests.

  15. Cobalt doped CuMnOx catalysts for the preferential oxidation of carbon monoxide

    Science.gov (United States)

    Dey, Subhashish; Dhal, Ganesh Chandra; Mohan, Devendra; Prasad, Ram; Gupta, Rajeev Nayan

    2018-05-01

    Carbon monoxide (CO) is a poisonous gas, recognized as a silent killer for the 21st century. It is produced from the partial oxidation of carbon containing compounds. The catalytic oxidation of CO receives a huge attention due to its applications in different fields. In the present work, hopcalite (CuMnOx) catalysts were synthesized using a co-precipitation method for CO oxidation purposes. Also, it was doped with the cobalt by varying concentration from 1 to 5wt%. It was observed that the addition of cobalt into the CuMnOx catalyst (by the deposition-precipitation method) improved the catalytic performance for the low-temperature CO oxidation. CuMnOx catalyst doped with 3wt% of cobalt exhibited most active performance and showed the highest activity than other cobalt concentrations. Different analytical tools (i.e. XRD, FTIR, BET, XPS and SEM-EDX) were used to characterize the as-synthesized catalysts. It was expected that the introduction of cobalt will introduce new active sites into the CuMnOx catalyst that are associated with the cobalt nano-particles. The order of calcination strategies based on the activity for cobalt doped CuMnOx catalysts was observed as: Reactive calcinations (RC) > flowing air > stagnant air. Therefore, RC (4.5% CO in air) route can be recommended for the synthesis of highly active catalysts. The catalytic activity of doped CuMnOx catalysts toward CO oxidation shows a correlation among average oxidation number of Mn and the position and the nature of the doped cobalt cation.

  16. Aluminum Oxide Formation On Fecral Catalyst Support By Electro-Chemical Coating

    Directory of Open Access Journals (Sweden)

    Yang H.S.

    2015-06-01

    Full Text Available FeCrAl is comprised essentially of Fe, Cr, Al and generally considered as metallic substrates for catalyst support because of its advantage in the high-temperature corrosion resistance, high mechanical strength, and ductility. Oxidation film and its adhesion on FeCrAl surface with aluminum are important for catalyst life. Therefore various appropriate surface treatments such as thermal oxidation, Sol, PVD, CVD has studied. In this research, PEO (plasma electrolytic oxidation process was applied to form the aluminum oxide on FeCrAl surface, and the formed oxide particle according to process conditions such as electric energy and oxidation time were investigated. Microstructure and aluminum oxide particle on FeCrAl surface after PEO process was observed by FE-SEM and EDS with element mapping analysis. The study presents possibility of aluminum oxide formation by electro-chemical coating process without any pretreatment of FeCrAl.

  17. The Complete Oxidation of Ethanol at Low Temperature over a Novel Pd-Ce/γ-Al2O3-TiO2 Catalyst

    International Nuclear Information System (INIS)

    Wang, Yanping; Zhao, Jinshuang; Wang, Xiaoli; Li, Zhe; Liu, Pengfei

    2013-01-01

    Pd-Ce/γ-Al 2 O 3 -TiO 2 catalysts were prepared by combined sol.gel and impregnation methods. Transmission electron microscopy, X-ray diffraction, H 2 -temperature-programmed reduction, O 2 -temperature-programmed desorption, and ethanol oxidation experiments were conducted to determine the properties of the catalysts. Addition of an optimal amount of Ce improved the performance of the Pd/γ-Al 2 O 3 -TiO 2 catalyst in promoting the complete oxidation of ethanol. The catalyst with 1% Ce exhibited the highest activity, and catalyzed complete oxidation of ethanol at 175 .deg. C; its selectivity to CO 2 reached 87%. Characterization results show that addition of appropriate amount of Ce could enrich the PdO species, and weaken the Pd-O bonds, thus enhancing oxidation ability of the catalyst. Meanwhile, the introduction of CeO 2 could make PdO better dispersed on γ-Al 2 O 3 -TiO 2 , which is beneficial for the improvement of the catalytic oxidation activity

  18. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2015-09-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

  19. Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

    Science.gov (United States)

    Tan, Qiang; Zhu, Haiyan; Guo, Shengwu; Chen, Yuanzhen; Jiang, Tao; Shu, Chengyong; Chong, Shaokun; Hultman, Benjamin; Liu, Yongning; Wu, Gang

    2017-08-31

    Deactivation of an anode catalyst resulting from the poisoning of CO ad -like intermediates is one of the major problems for methanol and ethanol electro-oxidation reactions (MOR & EOR), and remains a grand challenge towards achieving high performance for direct alcohol fuel cells (DAFCs). Herein, we report a new approach for the preparation of ultrafine cobalt-doped CeO 2 dots (Co-CeO 2 , d = 3.6 nm), which can be an effective anti-poisoning promoter for Pd catalysts towards MOR and EOR in alkaline media. Compared to Pd/CeO 2 and pure Pd, the hybrid Pd/Co-CeO 2 nanocomposite catalyst exhibited a much enhanced activity and remarkable anti-poisoning ability for both MOR and EOR. The nanocomposite catalyst showed much higher mass activity (4×) than a state-of-the-art PtRu catalyst. The promotional mechanism was elucidated using extensive characterization and density-functional theory (DFT). A bifunctional effect of the Co-CeO 2 dots was discovered to be due to (i) an enhanced electronic interaction between Co-CeO 2 and Pd dots and (ii) the increased oxygen storage capacity of Co-CeO 2 dots to facilitate the oxidation of CO ad . Therefore, the Pd/Co-CeO 2 nanocomposite appears to be a promising catalyst for advanced DAFCs with low cost and high performance.

  20. Nanosized spinel oxide catalysts for CO-oxidation prepared via CoMnMgAl quaternary hydrotalcite route

    Energy Technology Data Exchange (ETDEWEB)

    Mokhtar, M., E-mail: mmoustafa@kau.edu.s [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia); Basahel, S.N.; Al-Angary, Y.O. [Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, P.O. Box 80203 (Saudi Arabia)

    2010-03-18

    Catalytic activity of the Co-Mn-Mg-Al mixed oxide spinel catalysts was examined in CO oxidation by O{sub 2}. The prepared catalysts were characterized by chemical analysis (ICP), infrared spectroscopy (FTIR), thermal analysis (TG, DTG), powder X-ray diffraction (XRD), surface area measurements, and scanning electron microscopy (SEM).The calcined hydrotalcite-like precursor was composed of spinel-like Co-Mn-Mg-Al mixed oxide as the only XRD crystalline phases. The nanosized spinel oxide catalysts produced by calcination of hydrotalcites showed higher S{sub BET} than CoMn-hydrotalcite samples as calcination led to dehydroxylation and carbonate decomposition of anions in interlayer spaces. All the catalysts showed 100% CO conversion at high temperature even those calcined at 800 {sup o}C. A catalyst with Co/Mn = 4 and calcined at 500 {sup o}C showed 100% CO conversion at 160 {sup o}C. Moreover, this catalyst exhibited quite good durability without deactivation in 60 h stability test.

  1. Electrocatalytic Reduction-oxidation of Chlorinated Phenols using a Nanostructured Pd-Fe Modified Graphene Catalyst

    International Nuclear Information System (INIS)

    Shi, Qin; Wang, Hui; Liu, Shaolei; Pang, Lei; Bian, Zhaoyong

    2015-01-01

    A Pd-Fe modified graphene (Pd-Fe/G) catalyst was prepared by the Hummers oxidation method and bimetallic co-deposition method. The catalyst was then characterized by various characterization techniques and its electrochemical property toward the electrocatalytic reduction-oxidation of chlorinated phenols was investigated by using cyclic voltammetry and differential pulse voltammetry. The results of the characterization show that the Pd-Fe/G catalyst in which the weight proportion of Pd and Fe is 1:1 has an optimal surface performance. The diameter of the Pd-Fe particles is approximately 5.2 ± 0.3 nm, with a uniform distribution on the supporting graphene. This is smaller than the Pd particles of a Pd-modified graphene (Pd/G) catalyst. The Pd-Fe/G catalyst shows a higher electrocatalytic activity than the Pd/G catalyst for reductive dechlorination when feeding with hydrogen gas. The reductive peak potentials of −0.188 V, −0.836 V and −0.956 V in the DPV curves are attributed to the dechlorination of ortho-Cl, meta-Cl, and para-Cl in 2-chlorophenol, 3-chlorophenol and 4-chlorophenol, respectively. In accordance with an analysis of the frontier orbital theory, the order of ease of dechlorination with Pd-Fe/G catalyst is 2-chlorophenol > 3-chlorophenol > 4-chlorophenol. The Pd-Fe/G catalyst has a greater activity than the Pd/G catalyst in accelerating the two-electron reduction of O_2 to H_2O_2, which is attributed to the higher current of the reduction peak at approximately −0.40 V when feeding with oxygen gas. Therefore, the Pd-Fe/G catalyst exhibits a higher electrocatalytic activity than the Pd/G catalyst for the reductive dechlorination and acceleration of the two-electron reduction of O_2 to H_2O_2.

  2. Low-Temperature Oxidation of Dimethyl Ether to Polyoxymethylene Dimethyl Ethers over CNT-Supported Rhenium Catalyst

    Directory of Open Access Journals (Sweden)

    Qingde Zhang

    2016-03-01

    Full Text Available Due to its excellent conductivity, good thermal stability and large specific surface area, carbon nano-tubes (CNTs were selected as support to prepare a Re-based catalyst for dimethyl ether (DME direct oxidation to polyoxymethylene dimethyl ethers (DMMx. The catalyst performance was tested in a continuous flow type fixed-bed reactor. H3PW12O40 (PW12 was used to modify Re/CNTs to improve its activity and selectivity. The effects of PW12 content, reaction temperature, gas hourly space velocity (GHSV and reaction time on DME oxidation to DMMx were investigated. The results showed that modification of CNT-supported Re with 30% PW12 significantly increased the selectivity of DMM and DMM2 up to 59.0% from 6.6% with a DME conversion of 8.9%; besides that, there was no COx production observed in the reaction under the optimum conditions of 513 K and 1800 h−1. The techniques of XRD, BET, NH3-TPD, H2-TPR, XPS, TEM and SEM were used to characterize the structure, surface properties and morphology of the catalysts. The optimum amount of weak acid sites and redox sites promotes the synthesis of DMM and DMM2 from DME direct oxidation.

  3. Biodiesel production using alkali earth metal oxides catalysts synthesized by sol-gel method

    Directory of Open Access Journals (Sweden)

    Majid Mohadesi

    2014-03-01

    Full Text Available Biodiesel fuel is considered as an alternative to diesel fuel. This fuel is produced through transesterification reactions of vegetable oils or animal fat by alcohols in the presence of different catalysts. Recent studies on this process have shown that, basic heterogeneous catalysts have a higher performance than other catalysts. In this study different alkali earth metal oxides (CaO, MgO and BaO doped SiO2 were used as catalyst for the biodiesel production process. These catalysts were synthesis by using the sol-gel method. A transesterification reaction was studied after 8h by mixing corn oil, methanol (methanol to oil molar ratio of 16:1, and 6 wt. % catalyst (based on oil at 60oC and 600rpm. Catalyst loading was studied for different catalysts ranging in amounts from 40, 60 to 80%. The purity and yield of the produced biodiesel for 60% CaO/SiO2 was higher than other catalysts and at 97.3% and 82.1%, respectively.

  4. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2015-03-05

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

  5. Metal Oxide Supported Vanadium Substituted Keggin Type Polyoxometalates as Catalyst For Oxidation of Dibenzothiophene

    Science.gov (United States)

    Lesbani, Aldes; Novri Meilyana, Sarah; Karim, Nofi; Hidayati, Nurlisa; Said, Muhammad; Mohadi, Risfidian; Miksusanti

    2018-01-01

    Supported polyoxometalatate H4[γ-H2SiV2W10O40]·nH2O with metal oxide i.e. silica, titanium, and tantalum was successfully synthesized via wet impregnation method to form H4[γ-H2SiV2W10O40]·nH2O-Si, H4[γ-H2SiV2W10O40]·nH2O-Ti, and H4[γ-H2SiV2W10O40]·nH2O-Ta. Characterization was performed using FTIR spectroscopy, X-Ray analyses, and morphology analyses using SEM. All compounds were used as the catalyst for desulfurization of dibenzothiophene (DBT). Silica and titanium supported polyoxometalate H4[γ-H2SiV2W10O40]·nH2O better than tantalum due to retaining crystallinity after impregnation process. On the other hand, compound H H4[γ-H2SiV2W10O40]·nH2O-Ta showed high catalytic activity than other supported metal oxides for desulfurization of DBT. Optimization desulfurization process resulted in 99% conversion of DBT under a mild condition at 70 °C, 0.1 g catalyst, and reaction for 3 hours. Regeneration studies showed catalyst H4[γ-H2SiV2W10O40]·nH2O-Ti was remaining catalytic activity for desulfurization of DBT.

  6. Investigation of activity and selectivity of redox catalysts in oxidative ...

    African Journals Online (AJOL)

    Then, the different reaction conditions on this catalyst in a fluidized bed reactor ... In transient state experiments, methane feed without the presence of oxygen in the gas ... and the speed decrease, methane conversion decreases dramatically.

  7. Strategies for catalyst development: possibilities of the ``rational approach`` illustrated with partial oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, W.; Schedel-Niedrig, T.; Schloegl, R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany). Abt. Oberflaechenphysik

    1998-12-31

    The paper discusses two petrochemical selective oxidation reactions namely the practised formation of styrene (STY) and the desired oxidative functionalisation of propane. The present knowledge about the mode of operation of oxide catalysts is critically considered. The dehydrogenation of ethylbenzene (EB) should be described by an oxidehydration with water acting as oxidant. The potential role of the coke formed during catalytic reaction as co-catalyst will be discussed. Selective oxidation is connected with the participation of lattice oxygen mechanism which transforms unselective gas phase oxygen into selective oxygen. The atomistic description of this process is still quite unclear as well as the electron structural properties of the activated oxygen atom. The Role of solid state acidity as compared to the role of lattice oxygen is much less well investigated modern multiphase-multielement oxide (MMO) catalysts. The rationale is that the significant efforts made to improve current MMO systems by chemical modifications can be very much more fruitful when in a first step the mode of action of a catalyst is clarified on the basis of suitable experiments. Such time-consuming experiments at the beginning of a campaign for catalyst improvement pay back their investment in later stages of the project when strategies of chemical development can be derived on grounds of understanding. (orig.)

  8. Lithium/magnesium oxide catalyst and method of making

    Energy Technology Data Exchange (ETDEWEB)

    Lunsford, J.H.; Hinson, P.G.

    1991-07-16

    This patent describes a method for preparing a catalyst which is effective for converting methane to ethane and ethylene. It comprises mixing a solution of a magnesium alkoxide in an alcohol with a solution containing a source of lithium in an alcohol, to obtain a ratio of magnesium metal to lithium metal; hydrolyzing the magnesium alkoxide in the solution to form a gel; and calcining the gel to form a catalyst which is effective for converting methane to ethane and ethylene.

  9. Study of the oxides nature effect of rare and rare earth elements on the aluminium-chromium catalyst properties

    International Nuclear Information System (INIS)

    Dadashev, B.A.; Abbasov, S.G.; Sarydzhanov, A.A.; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

    1975-01-01

    Adsorption studies have shown that oxides of rare and rare earth elements REE appreciably influence the structure of aluminium-chrome catalyst. Alkaline promotors, unlike REE, contribute to the formation of developed contact surface. Electrophysical investigations show that oxides of rare elements introduced into the catalyst increase its conductivity and activation energy. As for REE oxides, they decrease the conductivity and increase the activation energy. Catalysts with developed surface and high conductivity are also more active in the reaction of isopentane dehydration

  10. o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

    Science.gov (United States)

    Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

    2016-10-07

    A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

  11. Factors responsible for activity of catalysts of different chemical types in the reaction of hydrogen oxidation

    International Nuclear Information System (INIS)

    Il'chenko, N.I.; Dolgikh, L.Yu.

    1985-01-01

    Reasons of differences in the kinetics and mechanism of the H 2 oxidation on optimum metallic (Pt), carbide (WC) and oxide (Co 3 O 4 ) catalysts are discussed. These differences lead to unequal specific activity. It is shown that the catalytic activity of the catalysts in question increases with respect to reactions of isotopic exchange and hydrogen oxidation with an increasing electron-donating ability of anat of the transition metal M on which H 2 is adsorbed. The possibility is considered of increasing the transition metal activity by introduction of additions to increase the electron-donating ability of M

  12. Role of Cu-Mg-Al mixed oxide catalysts in lignin depolymerization in supercritical ethanol

    NARCIS (Netherlands)

    Huang, X.; Ceylanpinar, A.; Koranyi, T.I.; Boot, M.D.; Hensen, E.J.M.

    2015-01-01

    We investigate the role of Cu-Mg-Al mixed oxides in depolymerization of soda lignin in supercritical ethanol. A series of mixed oxides with varying Cu content and (Cu+Mg)/Al ratio were prepared. The optimum catalyst containing 20 wt% Cu and having a (Cu+Mg)/Al ratio of 4 yielded 36 wt% monomers

  13. Calcium Oxide Supported on Monoclinic Zirconia as a Highly Active Solid Base Catalyst

    NARCIS (Netherlands)

    Frey, A.M.; Haasterecht, van T.; Jong, de K.P.; Bitter, J.H.

    2013-01-01

    Calcium oxide supported on ZrO2 is a highly active catalyst for base-catalyzed reactions such as aldol-type reactions and transesterification reactions. The role of key parameters during preparation, that is, impregnation versus precipitation, heat treatment, and metal oxide loading on the basicity

  14. Hydrogenation of Levulinic Acid over Nickel Catalysts Supported on Aluminum Oxide to Prepare γ-Valerolactone

    Directory of Open Access Journals (Sweden)

    Jie Fu

    2015-12-01

    Full Text Available Four types of nickel catalysts supported on aluminum oxide (Ni/Al2O3 with different nickel loadings were synthesized using the co-precipitation method and were used for the hydrogenation of levulinic acid (LA to prepare γ-valerolactone (GVL. The synthesized Ni/Al2O3 catalysts exhibited excellent catalytic activity in dioxane, and the activity of the catalysts was excellent even after being used four times in dioxane. The catalytic activity in dioxane as a solvent was found to be superior to the activity in water. Nitrogen physisorption, X-ray diffraction, and transmission electron microscopy were employed to characterize the fresh and used catalysts. The effects of the nickel loading, temperature, hydrogen pressure, and substrate/catalyst ratio on the catalytic activity were investigated.

  15. Phenol oxidation by a sequential CWPO-CWAO treatment with a Fe/AC catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Quintanilla, A. [Area de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid (Spain)]. E-mail: asun.quintanilla@uam.es; Fraile, A.F. [Area de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid (Spain); Casas, J.A. [Area de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid (Spain); Rodriguez, J.J. [Area de Ingenieria Quimica, Facultad de Ciencias, Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid (Spain)

    2007-07-31

    Catalytic wet peroxide oxidation (CWPO) of phenol with a homemade Fe/activated carbon (Fe/AC) catalyst has been studied in a stainless steel fixed-bed reactor at different operating conditions (T = 23-100 deg. C, P {sub T} = 1-8 atm, W = 0-2.5 g, and {tau} = 20-320 g{sub CAT} h/g{sub Phenol}). The results show that, thanks to the incorporation of Fe on the activated carbon, phenol conversion improved dramatically, reaching a 90% at 65 deg. C, 2 atm, and 40 g{sub CAT} h/g{sub Phenol}. However, TOC conversion values remain fairly low, (around 5% at 40 g{sub CAT} h/g{sub Phenol}), and no improvement was obtained with the inclusion of Fe. The presence of Fe seems to promote the nondesirable coupling reactions that take place in CWPO of phenol due to the condensation of the ring intermediates (the primary phenol oxidation products). These condensation products are quite refractory to CWPO at the conditions employed. Taking advantage of the high phenol conversions in CWPO and the high phenol mineralization in CWAO, along with the good stability of the Fe/AC catalyst, a CWPO-CWAO sequential treatment has been successfully performed by using a fixed-bed and trickle-bed reactor in series. A CWPO treatment at ambient conditions followed by a CWAO treatment at mild conditions (100 deg. C and 8 atm) is presented as high efficiency process for the decontamination of phenolic wastewaters.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  17. 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...

  18. Synthesis of cerium oxide catalysts supported on MCM-41 molecular sieve

    International Nuclear Information System (INIS)

    Souza, E.L.S.; Barros, T.R.B.; Sousa, B.V. de

    2016-01-01

    Porous materials have been widely studied as catalysts and catalyst support. The MCM-41 structure is the one that has been most studied because of its application possibilities in chemical processes. This work aimed to obtain and characterize cerium oxide catalysts supported on MCM-41 molecular sieve. The molecular sieve was synthesized by the conventional method with the following molar composition: 1 SiO2: 0.30 CTABr: NH3 11: 144 H2O. Then, 25% w/w cerium was incorporated into the MCM-41 using the wet impregnation process and the material obtained was activated by calcination. From the XRD patterns was confirmed the structure of the molecular sieve, and were identified the cerium oxide phases in its structure. The textural catalysts characteristics were investigated by isotherms of N2 adsorption/desorption (BET method). (author)

  19. Change in activity of catalysts for the oxidation of tritium during a fire event

    International Nuclear Information System (INIS)

    Iwai, Yasunori; Sato, Katsumi; Yamanishi, Toshihiko

    2012-01-01

    Highlights: ► We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalysts for tritium oxidation. ► At 423 K, no considerable decrease in catalytic activity was observed. ► At 293 K, considerable increase in catalytic activity was initially observed due to the effect of produced hydrogen. Then the temporary decrease was observed due mainly to the effect of produced moisture, however the activity was gradually recovered. - Abstract: The catalytic performance should be maintained in any off normal events. Fire accident is the typical off normal event. In the fusion plant, typical combustibles are evaluated to be polymeric low-halogen cables. Produced gases from burned low-halogen cable may affect the activity of catalysts for the oxidation of tritium. We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalyst using tritium gas. Our evaluation showed that ethylene, methane and benzene were major produced gases. The activity of catalysts for the oxidation of tritium during a fire event was evaluated using a commercial hydrophilic Pt/Al 2 O 3 catalyst and a commercial hydrophobic Pt-catalyst. The temperature of catalytic reactor was selected to be 423 and 293 K. At 423 K, no considerable decrease in catalytic activity was observed for both catalysts even in the presence of produced gases from burned low-halogen cable. At 293 K, considerable increase in catalytic activity was initially observed for both catalysts due to the effect of produced hydrogen. Then the temporary decrease was observed, however the catalytic activity was gradually recovered to be the original activity. Consequently, the irreversible decrease in activity of the catalysts during a fire event was not observed.

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

    Directory of Open Access Journals (Sweden)

    Niina Koivikko

    2018-02-01

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

  1. Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel

    International Nuclear Information System (INIS)

    Taufiq-Yap, Y.H.; Lee, H.V.; Hussein, M.Z.; Yunus, R.

    2011-01-01

    Calcium-based mixed oxides catalysts (CaMgO and CaZnO) have been investigated for the transesterification of Jatropha curcas oil (JCO) with methanol, in order to evaluate their potential as heterogeneous catalysts for biodiesel production. Both CaMgO and CaZnO catalysts were prepared by coprecipitation method of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at ∼ pH 8-9. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed desorption of CO 2 (CO 2 -TPD), scanning electron microscopy (SEM) and N 2 adsorption (BET). The conversion of JCO by CaMgO and CaZnO were studied and compared with calcium oxide (CaO), magnesium oxide (MgO) and zinc oxide (ZnO) catalysts. Both CaMgO and CaZnO catalysts showed high activity as CaO and were easily separated from the product. CaMgO was found more active than CaZnO in the transesterification of JCO with methanol. Under the suitable transesterification conditions at 338 K (catalyst amount = 4 wt. %, methanol/oil molar ratio = 15, reaction time = 6 h), the JCO conversion of more than 80% can be achieved over CaMgO and CaZnO catalysts. Even though CaO gave the highest activity, the conversion of JCO decreased significantly after reused for forth run whereas the conversion was only slightly lowered for CaMgO and CaZnO after sixth run.

  2. Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst.

    Science.gov (United States)

    Al-Hunaiti, Afnan; Niemi, Teemu; Sibaouih, Ahlam; Pihko, Petri; Leskelä, Markku; Repo, Timo

    2010-12-28

    In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.

  3. 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.

  4. Removal of carbonaceous deposits from the surface of cobalt-molybdate catalyst via oxidative regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Yoshimura, Y.; Furimsky, E.

    1986-10-01

    The oxidative regeneration of cobalt-molybdate catalyst used during the hydrodeoxygenation of a phenol solution and for hydrotreatment of Athabasca bitumen was carried out in a fixed-bed reactor. SO/sub 2/, CO and CO/sub 2/ were analysed as the major products. The surface area of the spent catalysts was the main factor influencing the initial rate of regeneration, i.e. the greater the surface area the higher the initial rate. A mechanism proposed includes 12 reactions which may play an important role in the overall burn-off of hydrotreatment catalysts. 10 refs., 4 figs., 3 tabs.

  5. Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships

    NARCIS (Netherlands)

    Wachs, I.E.; Jehng, J.M.; Deo, G.; Weckhuysen, B.M.; Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

    1997-01-01

    The oxidation of n-butane to maleic anhydride was investigated over a series of model-supported vanadia catalysts where the vanadia phase was present as a two-dimensional metal oxide overlayer on the different oxide supports (TiO2, ZrO2, CeO2, Nb2O5, Al2O3, and SiO2). No correlation was found

  6. Investigation of the oxidative ammonolysis of propylene on oxide catalysts containing molybdenum and using the response method

    International Nuclear Information System (INIS)

    Gadzhiev, K.N.; Adzhamov, K.Y.; Alkhazov, T.G.; Khanmamedova, A.K.

    1985-01-01

    The response method has been used to study the oxidative ammonolysis of propylene on MoO 3 and molybdenum oxide systems containing bismuth, silicon, and phosphorous ions. The response curves obtained for ammonia, propylene, CO 2 , acrolein, acrylonitrile in these systems are discussed and compared with individual molybdenum trioxide. It has been shown that the modifying action of ammonia on the catalyst surfaces determines the direction of the oxidative conversion of the propylene

  7. Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

    Science.gov (United States)

    Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

    2017-08-16

    Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

  8. Pd-Au/C catalysts with different alloying degrees for ethanol oxidation in alkaline media

    International Nuclear Information System (INIS)

    Qin, Yuan-Hang; Li, Yunfeng; Lv, Ren-Liang; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

    2014-01-01

    High alloyed Pd-Au/C catalyst is prepared through a rate-limiting strategy in water/ethylene glycol solution. Pd/C and low alloyed Pd-Au/C catalysts are prepared with trisodium citrate and sodium borohydride as stabilizing and reducing agents, respectively. Transmission electron microscopy (TEM) shows that the synthesized Pd(Au) particles are well dispersed on the catalysts. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) show that the high alloyed Pd-Au/C catalyst presents a relatively homogenous structure while the low alloyed Pd-Au/C catalyst presents a Pd-rich shell/Au-rich core structure. Electrochemical characterization shows that the low alloyed Pd-Au/C catalyst exhibits the best catalytic activity for ethanol oxidation reaction (EOR) in alkaline media, which could be attributed to its relatively large exposed Pd surface area as compared with the high alloyed Pd-Au/C catalyst due to its Pd-rich shell structure and its enhanced adsorption of OH ads as compared with Pd/C catalyst due to its core-shell structure

  9. Catalytic Oxidation of Propene over Pd Catalysts Supported on CeO2, TiO2, Al2O3 and M/Al2O3 Oxides (M = Ce, Ti, Fe, Mn

    Directory of Open Access Journals (Sweden)

    Sonia Gil

    2015-04-01

    Full Text Available In the following work, the catalytic behavior of Pd catalysts prepared using different oxides as support (Al2O3, CeO2 and TiO2 in the catalytic combustion of propene, in low concentration in excess of oxygen, to mimic the conditions of catalytic decomposition of a volatile organic compound of hydrocarbon-type is reported. In addition, the influence of different promoters (Ce, Ti, Fe and Mn when added to a Pd/Al2O3 catalyst was analyzed. Catalysts were prepared by the impregnation method and were characterized by ICP-OES, N2 adsorption, temperature-programmed reduction, temperature-programmed oxidation, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Catalyst prepared using CeO2 as the support was less easily reducible, due to the stabilization effect of CeO2 over the palladium oxides. Small PdO particles and, therefore, high Pd dispersion were observed for all of the catalysts, as confirmed by XRD and TEM. The addition of Ce to the Pd/Al2O3 catalysts increased the metal-support interaction and the formation of highly-dispersed Pd species. The addition of Ce and Fe improved the catalytic behavior of the Pd/Al2O3 catalyst; however, the addition of Mn and Ti decreased the catalytic activity in the propene oxidation. Pd/TiO2 showed the highest catalytic activity, probably due to the high capacity of this catalyst to reoxidize Pd into PdO, as has been found in the temperature-programmed oxidation (TPO experiments.

  10. Enhanced oxidation of naphthalene using plasma activation of TiO2/diatomite catalyst.

    Science.gov (United States)

    Wu, Zuliang; Zhu, Zhoubin; Hao, Xiaodong; Zhou, Weili; Han, Jingyi; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming

    2018-04-05

    Non-thermal plasma technology has great potential in reducing polycyclic aromatic hydrocarbons (PAHs) emission. But in plasma-alone process, various undesired by-products are produced, which causes secondary pollutions. Here, a dielectric barrier discharge (DBD) reactor has been developed for the oxidation of naphthalene over a TiO 2 /diatomite catalyst at low temperature. In comparison to plasma-alone process, the combination of plasma and TiO 2 /diatomite catalyst significantly enhanced naphthalene conversion (up to 40%) and CO x selectivity (up to 92%), and substantially reduced the formation of aerosol (up to 90%) and secondary volatile organic compounds (up to near 100%). The mechanistic study suggested that the presence of the TiO 2 /diatomite catalyst intensified the electron energy in the DBD. Meantime, the energized electrons generated in the discharge activated TiO 2 , while the presence of ozone enhanced the activity of the TiO 2 /diatomite catalyst. This plasma-catalyst interaction led to the synergetic effect resulting from the combination of plasma and TiO 2 /diatomite catalyst, consequently enhanced the oxidation of naphthalene. Importantly, we have demonstrated the effectiveness of plasma to activate the photocatalyst for the deep oxidation of PAH without external heating, which is potentially valuable in the development of cost-effective gas cleaning process for the removal of PAHs in vehicle applications during cold start conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

    DEFF Research Database (Denmark)

    Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

    2008-01-01

    A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient cond...... conditions; the reactions can be performed in an open flask and at room temperature. Benzaldehyde is even oxidised at a reasonable rate below -70 degrees C. Acrolein is oxidised to methyl acrylate in high yield using the same protocol.......A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

  12. Low temperature incineration of mixed wastes using bulk metal oxide catalysts

    International Nuclear Information System (INIS)

    Gordon, M.J.; Gaur, S.; Kelkar, S.; Baldwin, R.M.

    1996-01-01

    Volume reduction of low-level mixed wastes from former nuclear weapons facilities is a significant environmental problem. Processing of these materials presents unique scientific and engineering problems due to the presence of minute quantities of radionuclides which must be contained and concentrated for later safe disposal. Low-temperature catalytic incineration is one option that has been utilized at the Rocky Flats facility for this purpose. This paper presents results of research regarding evaluation of bulk metal oxides as catalysts for low-temperature incineration of carbonaceous residues which are typical by-products of fluidized bed combustion of mixed wastes under oxygen-lean conditions. A series of 14 metal oxides were screened in a thermogravimetric analyzer, using on-line mass spectrometry for speciation of reaction product gases. Catalyst evaluation criteria focused on the thermal-redox activity of the metals using both carbon black and PVC char as surrogate waste materials. Results indicated that metal oxides which were P-type semiconductor materials were suitable as catalysts for this application. Oxides of cobalt, molybdenum, vanadium, and manganese were found to be particularly stable and active catalysts under conditions specific to this process (T<650C, low oxygen partial pressures). Bench-scale evaluation of these metal oxides with respect to stability to chlorine (HCl) attack was carried out at 550C using a TG/MS system. Cobalt oxide was found to be resistant to metal loss in a HCl/He gaseous environment while metal loss from Mo, Mn, and V-based catalysts was moderate to severe. XRD and SEM/EDX analysis of spent Co catalysts indicated the formation of non-stoichiometric cobalt chlorides. Regeneration of chlorinated cobalt was found to successfully restore the low-temperature combustion activity to that of the fresh metal oxide

  13. Reduction of Nitrogen Oxides using zeolite catalysts exchanged with cobalt

    International Nuclear Information System (INIS)

    Garcia M, E.A.; Bustamante L, F.; Montes de C, C.

    1999-01-01

    The Selective Catalytic Reduction (SCR) of NOx by methane in excess oxygen was studied over several zeolite catalysts; namely cobalt loaded mordenite, ferrierite, SM-5 and the corresponding acid forms. When NO2 predominated n the NOx mixture the acid forms showed the highest N2 formation rates under dry conditions. Mordenite supported catalysts were the most active ones followed by ferrierite and ZSM-5. The most active Co-Mordenite catalyst was tested using a NOx mixture, containing mostly NO, under dry conditions and in the presence of water and SO2. The addition of 8 % water to the reaction mixture lead to a reversible deactivation, mainly at low temperatures. When the reaction mixture contained 60 ppm SO2, the N2 formation rate decreased about a half likely due to SO2 poisoning

  14. Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

    Science.gov (United States)

    Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

    1990-01-01

    Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

  15. In Situ Raman Spectroscopy of Supported Chromium Oxide Catalysts: Reactivity Studies with Methanol and Butane

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.

    1996-01-01

    The interactions of methanol and butane with supported chromium oxide catalysts under oxidizing and reducing conditions were studied by in situ Raman spectroscopy as a function of the specific oxide support (Al2O3, ZrO2, TiO2, SiO2, Nb2O5, 3% SiO2/TiO2, 3% TiO2/SiO2, and a physical mixture of SiO2

  16. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  17. Transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

    International Nuclear Information System (INIS)

    Jacobson, A.J.; Chianelli, R.R.; Pecoraro, T.A.

    1987-01-01

    A process is described for hydrorefining a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and in the presence of hydrogen with a catalyst obtained by heating one or more precursor salts at elevated temperature of at least about 150 0 C, in the presence of sulfur or one or more sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrorefine at least a portion of the feed

  18. 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)

  19. Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts

    International Nuclear Information System (INIS)

    Li, Zhe-Fei; Wang, Yuxuan; Botte, Gerardine G.

    2017-01-01

    Highlights: • A procedure to pretreat electrocatalysts to study the ammonia oxidation is provided. • N ads and O/OH ads were identified as the major deactivation species that prevent ammonia oxidatoin. • The electrocatalytic activity, thermodynamics, and possible deactivation mechanisms for ammonia oxidation were elucidated. • The onset potential for ammonia oxidation is related to the hydrogen binding energy of the catalyst. • Ammonia electro-oxidation involves a complex decoupled electron and proton transfer process. - Abstract: The ammonia electro-oxidation reaction (AOR) has been studied due to its promising applications in ammonia electrolysis, wastewater remediation, direct ammonia fuel cells, and sensors. However, it is difficult to compare and analyze the reported electrocatalytic activity of AOR reliably, likely due to the variation in catalyst synthesis, electrode composition, electrode morphology, and testing protocol. In this paper, the electro-oxidation of ammonia on different carbon-supported precious metal nanoparticle catalysts was revisited. The effect of experimental conditions, electrochemical test parameters, electrocatalytic activity, thermodynamics, and possible deactivation mechanism of the catalysts were investigated. Pt/C catalyst possesses the highest electrocatalytic activity, while Ir/C and Rh/C show lower overpotential. The onset potential of the AOR is related to the hydrogen binding energy of the catalyst. N ads is one major cause of deactivation accompanied with the formation of surface O/OH ads at high potentials. The coulombic efficiency of N ads formation on Pt is about 1% initially and gradually decreases with reaction time. Increase in ammonia concentration leads to increase in current density, while increase in hydroxyl ions concentration can enhance the current density and reduce the overpotential simultaneously. The slopes of AOR onset potential and hydrogen adsorption/desorption potential of Pt/C as a function of p

  20. ETHANOL OXIDATION OVER AU/TIO2 CATALYSTS

    African Journals Online (AJOL)

    DR. AMINU

    The adsorption and reaction of ethanol over Au/TiO2 catalysts was investigated using pulse ... the surface disappears, so the mechanism reverts to a decomposition pathway, producing methane, ... allowed to flow at a rate of 30 ml per minutes.

  1. Modified calcium oxide as stable solid base catalyst for Aldol

    Indian Academy of Sciences (India)

    A highly efficient and stable solid-base catalyst for Aldol condensation was prepared by modifying commercial CaO with benzyl bromide in a simple way. It was found that modified CaO can effectively catalyse the Aldol condensation of cyclohexanone and benzaldehyde, as well as various benzaldehydes, to produce ...

  2. Modified calcium oxide as stable solid base catalyst for Aldol ...

    Indian Academy of Sciences (India)

    A highly efficient and stable solid-base catalyst for Aldol condensation was ... was bonded on surface of CaO chemically and almost no Ca(OH)2 formed during the modification process. ... cation, corrosion and waste generation attract great.

  3. The nature of the potassium compound acting as a promoter in iron-alumina catalysts for ammonia synthesis

    NARCIS (Netherlands)

    van Ommen, J.G.; Bolink, W.J.; Prasad, J.; Mars, P.

    1975-01-01

    The chemical form of the potassium promoter on an iron-alumina catalyst during ammonia synthesis has been studied by two methods, viz, (i) the measurement of the equilibrium constant of the process KNH2 + H2 KH + NH3, and (ii) chemical analysis of the used catalyst. The equilibrium constant

  4. Transesterification Of Kapok Oil Using Calcium Oxide Catalyst Methyl Esters Yield With Catalyst Loading

    Directory of Open Access Journals (Sweden)

    Yunusa Tukur

    2015-08-01

    Full Text Available Abstract This investigation was necessitated to find other feedstocks for biodiesel production that would not compete with food. Kapok oil with 0.8 FFA was transesterified with methanol using a heterogeneous catalyst CaO to determine its potential for biodiesel production. Methyl esters yields of 70.4 65.6 78.2 71.9 and 72.5 were obtained with catalyst loading of 0.8 1.2 1.6 2.0 and 2.4 wt. of oil. The products had high compositions of FFA and alcohols which indicates that the oil require more esterification to reduce the feedstock FFA far below 0.8. Some unsaturated hydrocarbons such as alkenes and alkynes were also formed which could make the products unstable.

  5. 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

  6. 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.

  7. Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

    Science.gov (United States)

    McBriarty, Martin E.

    Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

  8. Magnesium oxide prepared via metal-chitosan complexation method: Application as catalyst for transesterification of soybean oil and catalyst deactivation studies

    Science.gov (United States)

    Almerindo, Gizelle I.; Probst, Luiz F. D.; Campos, Carlos E. M.; de Almeida, Rusiene M.; Meneghetti, Simoni M. P.; Meneghetti, Mario R.; Clacens, Jean-Marc; Fajardo, Humberto V.

    2011-10-01

    A simple method to prepare magnesium oxide catalysts for biodiesel production by transesterification reaction of soybean oil with ethanol is proposed. The method was developed using a metal-chitosan complex. Compared to the commercial oxide, the proposed catalysts displayed higher surface area and basicity values, leading to higher yield in terms of fatty acid ethyl esters (biodiesel). The deactivation of the catalyst due to contact with CO2 and H2O present in the ambient air was verified. It was confirmed that the active catalytic site is a hydrogenocarbonate adsorption site.

  9. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    International Nuclear Information System (INIS)

    Sawada, Kayo; Hirabayashi, Daisuke; Enokida, Youichi

    2013-01-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U 3 O 8 without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  10. Chemoselective Oxidation of Bio-Glycerol with Nano-Sized Metal Catalysts

    DEFF Research Database (Denmark)

    Li, Hu; Kotni, Ramakrishna; Zhang, Qiuyun

    2015-01-01

    to selectively oxidize glycerol and yield products with good selectivity is the use of nano-sized metal particles as heterogeneous catalysts. In this short review, recent developments in chemoselective oxidation of glycerol to specific products over nano-sized metal catalysts are described. Attention is drawn...... to various reaction parameters such as the type of the support, the size of the metal particles, and the acid/base properties of the reaction medium which were illustrated to largely influence the activity of the nanocatalyst and selectivity to the target product. - See more at: http...

  11. 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%.

  12. Highly Efficient Gas-Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate Vanadium Phosphorus Oxide Catalyst.

    Science.gov (United States)

    Li, Xiukai; Ko, Jogie; Zhang, Yugen

    2018-02-09

    Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. In this study, a plate vanadium phosphorus oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent catalyzes furfural oxidation to MAnh in the gas phase. The plate catalyst-denoted as VPO HT -has a preferentially exposed (200) crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 °C reaction temperature with air as an oxidant, about 90 % yield of MAnh was obtained at 10 vol % of furfural in the feed, a furfural concentration value that is much higher than those (<2 vol %) reported for other catalytic systems. The catalyst showed good long-term stability and there was no decrease in activity or selectivity for MAnh during the time-on-stream of 25 h. The high efficiency and catalyst stability indicate the great potential of this system for the synthesis of maleic anhydride from renewable furfural. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

    International Nuclear Information System (INIS)

    Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

  14. Facile preparation of a Pt/Prussian blue/graphene composite and its application as an enhanced catalyst for methanol oxidation

    International Nuclear Information System (INIS)

    Wang, Zonghua; Shi, Guoyu; Xia, Jianfei; Xia, Yanzhi; Zhang, Feifei; Xia, Lin; Song, Daimin; Liu, Jingquan; Li, Yanhui; Xia, Linhua; Brito, Manuel E.

    2014-01-01

    Graphical abstract: - Highlights: • Pt/Prussian blue/graphene catalyst was easily synthesized by the sequential electrodeposition method. • Prussian blue can promote the homogeneous growth of small Pt nanoparticles. • The as-made catalyst exhibited enhanced electro-catalytic performance for methanol oxidation. • The interplay of Prussian blue and Pt plays a significant role in reducing CO poisoning of the catalyst. - Abstract: Graphene nanosheets (GN) are modified by electrodeposition of Prussian blue (PB) followed by shape-regulated depositing of small Pt nanoparticles via the interaction between PB and PtCl 6 2− to form a novel catalyst Pt/PB/GN. The Pt/PB/GN composite exhibits significantly enhanced electrocatalytic activity with a mass activity of 445 mA mg −1 Pt (at 0.68 V vs. SCE) and high stability towards methanol oxidation. The high catalytic activity can be attributed to the unique porous architecture and peculiar electrical property of Prussian blue integrated with graphene layers which can not only well accommodate Pt nanoparticles but also provide multidimensional pathways to facilitate the mass and electron transport for methanol oxidation. This strategy can be readily extended to fabrication of other graphene-based hybrid supports for precious metal catalysts in fuel cell applications

  15. Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite Catalysts: A Review

    KAUST Repository

    Hong, Eunpyo

    2015-11-02

    1,3-Butadiene, an important raw material for a variety of chemical products, can be produced via the oxidative dehydrogenation (ODH) of n-butenes over multicomponent oxide catalysts based on bismuth molybdates and ferrites. In this review, the basic concept, reaction mechanism, and catalysts typically used in an ODH reaction are discussed. © 2015, Springer Science+Business Media New York.

  16. ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

    Science.gov (United States)

    Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

    2018-04-01

    Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

  17. Structure of alumina supported vanadia catalysts for oxidative dehydrogenation of propane prepared by flame spray pyrolysis

    DEFF Research Database (Denmark)

    Høj, Martin; Jensen, Anker Degn; Grunwaldt, Jan-Dierk

    2013-01-01

    .%. The catalysts were subsequently characterized by BET surface area, X-ray diffraction (XRD), Raman, UV–vis diffuse reflectance and X-ray absorption spectroscopy (XAS) as well as measurement of the catalytic performance. The catalysts had specific surface areas from 143 to 169 m2/g corresponding to average......A series of five vanadia on alumina catalysts for oxidative dehydrogenation of propane to propene were synthesized by flame spray pyrolysis (FSP) using vanadium(III)acetylacetonate and aluminium(III)acetylacetonate dissolved in toluene as precursors. The vanadium loading was 2, 3, 5, 7.5 and 10wt...... X-ray absorption near edge structure (XANES) spectroscopy showed that the vanadia can be reduced when operating at low oxygen concentrations. The catalyst performance was determined in fixed bed reactors with an inlet gas composition of C3H8/O2/N2=5/25/70. The main products were propene, CO and CO2...

  18. 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.

  19. 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

  20. 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.)

  1. Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

    Science.gov (United States)

    Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

    2017-06-28

    Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

  2. 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.

  3. Hydrogen purification for fuel cell by copper promoted gold catalysts; Purificacao de hidrogenio para pilha a combustivel utilizando catalisadores de ouro promovidos com cobre

    Energy Technology Data Exchange (ETDEWEB)

    Mozer, Thiago S.; Vieira, Carlos T.P.; Passos, Fabio B. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil); Dziuba, Dominika A. [Hochschule Mannheim (Germany)

    2008-07-01

    Copper promoted gold catalysts were studied for hydrogen purification through selective CO oxidation. The Cu acted as a selectivity promoter favoring the CO conversion and decreasing the H{sub 2} consumption. The deposition-precipitation method, used to prepare the samples generated small and well dispersed gold particles, as the UV-vis DRS spectra did not show the 'plasmon' band, which indicates that the samples are active for SELOX. The activity tests showed high CO conversion, the bimetallic 2,5%Au-0,5%Cu/Al{sub 2}O{sub 3} catalyst showed the best behavior in the tested condition, 95% of CO conversion and 75% of selectivity at 50 deg C. Increasing the O{sub 2} content in the feedstream the CO conversion also increased, although the selectivity decreased. (author)

  4. Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

    International Nuclear Information System (INIS)

    Muhammad, Yaseen; Lu Yingzhou; Shen Chong; Li Chunxi

    2011-01-01

    Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 o C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al 2 O 3 , Ni-Mo/Al 2 O 3 , Ru-Co-Mo/Al 2 O 3 and Ru-Ni-Mo/Al 2 O 3 were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N 2 adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al 2 O 3 catalyst at 380 o C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al 2 O 3 > Ni-Mo/Al 2 O 3 > Ru-Co-Mo/Al 2 O 3 > Co-Mo/Al 2 O 3 at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT.

  5. Dibenzothiophene hydrodesulfurization over Ru promoted alumina based catalysts using in situ generated hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Muhammad, Yaseen; Shen, Chong; Li, Chunxi [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Lu, Yingzhou [College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    2011-02-15

    Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-400 C using in situ generated hydrogen coupled with the effect of selected organic additives for the first time. Four kinds of alumina based catalysts i.e. Co-Mo/Al{sub 2}O{sub 3}, Ni-Mo/Al{sub 2}O{sub 3}, Ru-Co-Mo/Al{sub 2}O{sub 3} and Ru-Ni-Mo/Al{sub 2}O{sub 3} were used for the desulfurization process, which were prepared following incipient impregnation method with fixed metal loadings (wt.%) of Co, Ni, Mo and Ru. The surface area, average pore diameter and pore volume distribution of the fresh and used catalysts were measured by N{sub 2} adsorption using BET method. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Addition and mutual reaction of specific quantities of water and ethanol provided the necessary in situ hydrogen for the desulfurization reaction. Organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine did impinge the HDS activity of the catalysts in different ways. Liquid samples from reaction products were quantitatively analyzed by HPLC technique while qualitative analyses were made using GC-MS. Both of these techniques showed that Ni-based catalysts were more active than Co-based ones at all conditions. Moreover, incorporation of Ru to both Co and Ni-based catalysts greatly promoted desulfurization activity of these catalysts. DBT conversion of up to 84% was achieved with Ru-Ni-Mo/Al{sub 2}O{sub 3} catalyst at 380 C temperature for 11 h. Catalyst systems followed the HDS activity order as: Ru-Ni-Mo/Al{sub 2}O{sub 3}> Ni-Mo/Al{sub 2}O{sub 3}> Ru-Co-Mo/Al{sub 2}O{sub 3}> Co-Mo/Al{sub 2}O{sub 3} at all conditions. Cost effectiveness, mild operating conditions and reasonably high catalytic activity using in situ generated hydrogen mechanism proved our process to be useful for HDS of DBT. (author)

  6. Surface heterogeneity and ionization of Cs promoter in carbon-based ruthenium catalyst for ammonia synthesis

    International Nuclear Information System (INIS)

    Kotarba, Andrzej; Dmytrzyk, Jaromir; Rarog-Pilecka, Wioletta; Kowalczyk, Zbigniew

    2003-01-01

    Second-generation ammonia synthesis cesium-doped ruthenium catalyst supported on turbostratic carbon was investigated by the species resolved thermal alkali desorption method (SR-TAD). Energetic barriers for cesium ions (2.86 eV), ground state (1.96 eV) and electronically excited atoms (5.76 eV) desorbing from the Cs-Ru/C catalyst were determined. In the case of ruthenium-free Cs/C system, cesium desorbs as ground state atoms only, with an energy barrier of 2.87 eV. The work functions determined by the thermionic emission of electrons from Cs/C and Cs-Ru/C were of the same value (2.9 eV). It was concluded that ruthenium induces heterogeneous distribution of cesium on the catalyst surface. The promoter stability is reduced on low work function areas and its surface ionization on high work function areas opens the ionic desorption channel. The Cs desorption from the catalyst is discussed in terms of the literature data for the cesium/graphite system

  7. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization

    Directory of Open Access Journals (Sweden)

    Sonali Sengupta

    2013-12-01

    Full Text Available The oxidation of catechol was studied in an eco-friendly process with commercial titanium silicate-1 (TS-1 catalyst and hydrogen peroxide as oxidant in absence of all mass transfer effects. The process was opti-mized by Box-Behnken design in terms of three independent process variables such as reaction tempera-ture, moles of hydrogen peroxide per mole of catechol and catalyst amount whose optimum values of the process variables were found to be 60 °C, 13.2 and 1.24 g respectively for maximum conversion of 75.8 %. The effects of different process parameters such as mole ratio of hydrogen peroxide to catechol, catalyst par-ticle size, catalyst amount, temperature and reaction time were studied. A pseudo first order kinetic model was fitted with the experimental rate data. The apparent activation energy for the reaction was found to be 11.37 kJ/mole.  © 2013 BCREC UNDIP. All rights reservedReceived: 22nd April 2013; Revised: 25th October 2013; Accepted: 1st November 2013[How to Cite: Sengupta, S., Ghosal, D., Basu, J.K. (2013. Oxidation of Catechol using Titanium Silicate (TS-1 Catalyst: Modeling and Optimization. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (2: 167-177. (doi:10.9767/bcrec.8.2.4759.167-177][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.2.4759.167-177

  8. Application in industry and energy production of active carbon/cobalt catalyst for nitrogen oxide neutralization

    International Nuclear Information System (INIS)

    Mekhandzhiev, D.; Nikolov, R.; Lyutskanov, L.; Dushanov, D.; Lakov, L.

    1997-01-01

    A new material for neutralization of nitrogen oxides is presented. Two or three metals containing catalysts with a good activity and selectivity towards NO x have been obtained. Preparation of carbon catalysts by deposition of the active phase precursor on the initial carbon material prior to activation is considered as the most promising method. An active carbon-based catalyst (AC/Co) has been synthesized Apricot shells preliminary impregnated with a water-alcohol solution of Co nitrate have been used as initial carbon material. after drying they have been subjected to one-phase steam pyrolysis using a fix-bed reactor. The catalyst thus obtained has a specific surface area (BET) of 53 m 2 g -1 , a favorable mesopore volume/total volume ratio (about 0.85) determined by nitrogen adsorption, a suitable mesopore distribution, about 70% of the mesopores being characterized by r p larger than 25 A and a high dispersion of the Co oxide phase. In addition the catalyst possesses the necessary mechanical resistance. The catalyst has exhibited a high activity with respect to NO x reduction with CO at low temperatures (at 150-250 o C which are the temperatures of industrial flue gases, nO conversion up to 60-95% occurs) and a high selectivity. No presence of H 2 O has been established over the whole temperature range (100-300 o C). An additional advantage of the catalyst is the fact that the amount of CO above 150 o C is lower than the stoichiometric which indicates parallel participation in the process of both the active phase and the support (active carbon) It is also important that the presented catalyst has a low price due to the use of waste products from agriculture and the elimination of special thermal treatment of the supported Co nitrate. There are possibilities of using of other organic wastes from agriculture as well as wastes obtained during flotation of coal. (author)

  9. Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

    Science.gov (United States)

    Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

    2015-07-21

    The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

  10. Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon

    2012-02-01

    Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

  11. Effects of precursor and sulfation on OMS-2 catalyst for oxidation of ethanol and acetaldehyde at low temperatures.

    Science.gov (United States)

    Wang, Renhu; Li, Junhua

    2010-06-01

    Volatile organic compounds (VOCs) emitted from many industrial processes and transportation activities are major organic pollutants in the atmosphere and toxic to human health. Octahedral molecular sieve (OMS-2) catalysts with different precursors and sulfate-acidified OMS-2 catalysts were synthesized using refluxing methods. The catalysts were investigated on complete oxidation of ethanol and acetaldehyde, and both demonstrated good reactivity. However, acidification resulted in a decrease in activity. OMS-2 catalyst using MnSO(4) as precursor exhibited the best catalytic performance and, thus, was selected for catalyst deactivation by sulfur dioxide. The results of this study suggested that the Mn-O bond of OMS-2 catalysts was the main determinant of the catalytic activity toward oxygenated VOC oxidation and weaker acid sites benefited higher acetaldehyde selectivity. Catalyst deactivation resulted from a strong but slow chemical interaction between the Mn-O bond and sulfur dioxide, probably forming manganese sulfate.

  12. A study on production of biodiesel using a novel solid oxide catalyst derived from waste.

    Science.gov (United States)

    Majhi, Samrat; Ray, Srimanta

    2016-05-01

    The issues of energy security, dwindling supply and inflating price of fossil fuel have shifted the global focus towards fuel of renewable origin. Biodiesel, having renewable origin, has exhibited great potential as substitute for fossil fuels. The most common route of biodiesel production is through transesterification of vegetable oil in presence of homogeneous acid or base or solid oxide catalyst. But, the economics of biodiesel is not competitive with respect to fossil fuel due to high cost of production. The vegetable oil waste is a potential alternative for biodiesel production, particularly when disposal of used vegetable oil has been restricted in several countries. The present study evaluates the efficacy of a low-cost solid oxide catalyst derived from eggshell (a food waste) in transesterification of vegetable oil and simulated waste vegetable oil (SWVO). The impact of thermal treatment of vegetable oil (to simulate frying operation) on transesterification using eggshell-derived solid oxide catalyst (ESSO catalyst) was also evaluated along with the effect of varying reaction parameters. The study reported that around 90 % biodiesel yield was obtained with vegetable oil at methanol/oil molar ratio of 18:1 in 3 h reaction time using 10 % ESSO catalyst. The biodiesel produced with ESSO catalyst from SWVO, thermally treated at 150 °C for 24 h, was found to conform with the biodiesel standard, but the yield was 5 % lower compared to that of the untreated oil. The utilization of waste vegetable oil along with waste eggshell as catalyst is significant for improving the overall economics of the biodiesel in the current market. The utilization of waste for societal benefit with the essence of sustainable development is the novelty of this work.

  13. Advances in Base-Free Oxidation of Bio-Based Compounds on Supported Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Robert Wojcieszak

    2017-11-01

    Full Text Available The oxidation of bio-based molecules in general, and of carbohydrates and furanics in particular, is a highly attractive process. The catalytic conversion of renewable compounds is of high importance. Acids and other chemical intermediates issued from oxidation processes have many applications related, especially, to food and detergents, as well as to pharmaceutics, cosmetics, and the chemical industry. Until now, the oxidation of sugars, furfural, or 5-hydroxymethylfurfural has been mainly conducted through biochemical processes or with strong inorganic oxidants. The use of these processes very often presents many disadvantages, especially regarding products separation and selectivity control. Generally, the oxidation is performed in batch conditions using an appropriate catalyst and a basic aqueous solution (pH 7–9, while bubbling oxygen or air through the slurry. However, there is a renewed interest in working in base-free conditions to avoid the production of salts. Actually, this gives direct access to different acids or diacids without laborious product purification steps. This review focuses on processes applying gold-based catalysts, and on the catalytic properties of these systems in the base-free oxidation of important compounds: C5–C6 sugars, furfural, and 5-hydroxymethylfurfural. A better understanding of the chemical and physical properties of the catalysts and of the operating conditions applied in the oxidation reactions is essential. For this reason, in this review we put emphasis on these most impacting factors.

  14. Transesterification of Jatropha curcas crude oil to biodiesel on calcium lanthanum mixed oxide catalyst: Effect of stoichiometric composition

    International Nuclear Information System (INIS)

    Taufiq-Yap, Yun Hin; Teo, Siow Hwa; Rashid, Umer; Islam, Aminul; Hussien, Mohd Zobir; Lee, Keat Teong

    2014-01-01

    Highlights: • Biodiesel synthesis from Jatropha curcas oil catalyzed by CaO–La 2 O 3 mixed oxide. • Effects of Ca-to-La ratio, catalyst concentration, methanol/oil ratio and reaction temperature were optimized. • Biodiesel yield >85% was achieved at 65 °C temperature. • CaO–La 2 O 3 catalyst can be easy regenerated. - Abstract: Heterogeneous solid mixed oxide (CaO–La 2 O 3 ) catalysts with different molar ratios of calcium to lanthanum (Ca-to-La) were synthesized by co-precipitation method. The synthesized solid CaO–La 2 O 3 mixed metal oxide catalysts were utilized in transesterification of Jatropha curcus oil as feedstock to produce biodiesel. Under the optimized conditions at 65 °C, 4% catalyst dose with 24:1 MeOH to Jatropha oil molar ratio, the transesterification reaction exhibited 86.51% of biodiesel yield. The prepared catalysts were characterized using various techniques such as X-ray diffraction (XRD), nitrogen sorption with Brunauer–Emmer–Teller (BET) method, temperature-programmed desorption of CO 2 (CO 2 -TPD) and scanning electron microscopy (SEM). Influence of Ca-to-La atomic ratio in the mixed metal oxide catalyst, catalyst amount, methanol to oil molar ratio, reaction time, different oils on the fatty acid methyl ester (FAME) yield were appraised. Different catalyst regeneration procedures were also performed to investigate the reusability of the CaO–La 2 O 3 catalyst

  15. [Synergetic effects of silicon carbide and molecular sieve loaded catalyst on microwave assisted catalytic oxidation of toluene].

    Science.gov (United States)

    Wang, Xiao-Hui; Bo, Long-Li; Liu, Hai-Nan; Zhang, Hao; Sun, Jian-Yu; Yang, Li; Cai, Li-Dong

    2013-06-01

    Molecular sieve loaded catalyst was prepared by impregnation method, microwave-absorbing material silicon carbide and the catalyst were investigated for catalytic oxidation of toluene by microwave irradiation. Research work examined effects of silicon carbide and molecular sieve loading Cu-V catalyst's mixture ratio as well as mixed approach changes on degradation of toluene, and characteristics of catalyst were measured through scanning electron microscope, specific surface area test and X-ray diffraction analysis. The result showed that the fixed bed reactor had advantages of both thermal storage property and low-temperature catalytic oxidation when 20% silicon carbide was filled at the bottom of the reactor, and this could effectively improve the utilization of microwave energy as well as catalytic oxidation efficiency of toluene. Under microwave power of 75 W and 47 W, complete-combustion temperatures of molecular sieve loaded Cu-V catalyst and Cu-V-Ce catalyst to toluene were 325 degrees C and 160 degrees C, respectively. Characteristics of the catalysts showed that mixture of rare-earth element Ce increased the dispersion of active components in the surface of catalyst, micropore structure of catalyst effectively guaranteed high adsorption capacity for toluene, while amorphous phase of Cu and V oxides increased the activity of catalyst greatly.

  16. Formic Acid Modified Co3O4-CeO2 Catalysts for CO Oxidation

    Directory of Open Access Journals (Sweden)

    Ruishu Shang

    2016-03-01

    Full Text Available A formic acid modified catalyst, Co3O4-CeO2, was prepared via facile urea-hydrothermal method and applied in CO oxidation. The Co3O4-CeO2-0.5 catalyst, treated by formic acid at 0.5 mol/L, performed better in CO oxidation with T50 obtained at 69.5 °C and T100 obtained at 150 °C, respectively. The characterization results indicate that after treating with formic acid, there is a more porous structure within the Co3O4-CeO2 catalyst; meanwhile, despite of the slightly decreased content of Co, there are more adsorption sites exposed by acid treatment, as suggested by CO-TPD and H2-TPD, which explains the improvement of catalytic performance.

  17. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull [Yeungnam University, Gyeongsan (Korea, Republic of)

    2016-02-15

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  18. Magnetically Separable Iron Oxide Nanoparticles: An Efficient and Reusable Catalyst for Imino Diels-Alder Reaction

    International Nuclear Information System (INIS)

    Basavegowda, Nagaraj; Mishra, Kanchan; Lee, Yong Rok; Joh, Young-Gull

    2016-01-01

    Iron oxide nanoparticles were synthesized using Saururus chinensis (S. chinensis) leaf extract as a reducing and stabilizing agent via ultrasonication. The size, morphology, crystallinity, elemental composition, weight loss, surface chemical state, and magnetic properties of the synthesized nanoparticles were investigated. The synthe-sized nanoparticles were used as an efficient and recyclable catalyst for the synthesis of a variety of 2-methyl-4-substituted-1,2,3,4-tetrahydroquinoline derivatives by the imino Diels-Alder reaction. After the reaction, the catalyst was recovered by an external magnetic field. The recovered catalyst was then reused in a subsequent reaction under identical conditions. The recycled iron oxide nanoparticles (IONPs) were reused five times with-out any significant loss of catalytic activity.

  19. Biomass Derived Chemicals: Furfural Oxidative Esterification to Methyl-2-furoate over Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Maela Manzoli

    2016-07-01

    Full Text Available The use of heterogeneous catalysis to upgrade biomass wastes coming from lignocellulose into higher value-added chemicals is one of the most explored subjects in the prospective vision of bio-refinery. In this frame, a lot of interest has been driven towards biomass-derived building block molecules, such as furfural. Gold supported catalysts have been successfully proven to be highly active and selective in the furfural oxidative esterification to methyl-2-furoate under mild conditions by employing oxygen as benign oxidant. Particular attention has been given to the studies in which the reaction occurs even without base as co-catalyst, which would lead to a more green and economically advantageous process. The Au catalysts are also stable and quite easily recovered and represent a feasible and promising route to efficiently convert furfural to methyl-2-furoate to be scaled up at industrial level.

  20. Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts

    International Nuclear Information System (INIS)

    Wachs, I.E.; Fiato, R.A.; Chersich, C.C.

    1986-01-01

    A catalyst is described comprising iron carbide supported on a surface modified titania wherein the support comprises an oxide of a metal selected form the group consisting of niobium, vanadium, tantalum or mixture thereof supported on the titania wherein at least a portion of the supported oxide of niobium, vanandium, tantalum or mixture is in a non-crystalline form. The amount of the supported oxide ranges from about 0.5 to 25 weight percent metal oxide on the titania support based on the total support composition and the catalyst contains at least about 2 milligrams of iron, calculated as Fe/sub 2/O/sub 3/, per square meter of support surface

  1. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

    Science.gov (United States)

    Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

    2017-01-01

    Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  2. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

    Directory of Open Access Journals (Sweden)

    Ana Franco

    2017-07-01

    Full Text Available Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc. have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  3. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    Science.gov (United States)

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  4. Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation

    Directory of Open Access Journals (Sweden)

    Dimitrios Delimaris

    2017-11-01

    Full Text Available MnOx-CeO2 mixed oxides are considered efficient oxidation catalysts superior to the corresponding single oxides. Although these oxides have been the subject of numerous studies, their fundamental performance indicators, such as turnover frequency (TOF or specific activity, are scarcely reported. The purpose of the present work is to investigate the effect of catalyst composition on the concentration of active sites and intrinsic activity in ethanol oxidation by the employment of temperature-programmed desorption and oxidation of isotopically-labelled ethanol, 12CH313CH2OH. The transformation pathways of preadsorbed ethanol in the absence of gaseous oxygen refer to dehydrogenation to acetaldehyde followed by its dissociation combined with oxidation by lattice oxygen. In the presence of gaseous oxygen, lattice oxygen is rapidly restored and the main products are acetaldehyde, CO2, and water. CO2 forms less easily on mixed oxides than on pure MnOx. The TOF of ethanol oxidation has been calculated assuming that the amount of adsorbed ethanol and CO2 produced during temperature-programmed oxidation (TPO is a reliable indicator of the concentration of the active sites.

  5. Propan-1-ol Oxidation Reaction on Au/TiO2 Catalysts

    African Journals Online (AJOL)

    MBI

    2014-11-27

    Nov 27, 2014 ... a decomposition pathway, producing CO2 and H2O. However, the presence of gold ... complete oxidation reaction of propan-1-ol on the catalysts. Keywords: Gold Catalysis ... flowed at a rate of 30 mL min-1. Propan- o-l was.

  6. Removal of toluene by sequential adsorption-plasma oxidation: Mixed support and catalyst deactivation.

    Science.gov (United States)

    Qin, Caihong; Huang, Xuemin; Zhao, Junjie; Huang, Jiayu; Kang, Zhongli; Dang, Xiaoqing

    2017-07-15

    A sequential adsorption-plasma oxidation system was used to remove toluene from simulated dry air using γ-Al 2 O 3 , HZSM-5, a mixture of the two materials or their supported Mn-Ag catalyst as adsorbents under atmospheric pressure and room temperature. After 120min of plasma oxidation, γ-Al 2 O 3 had a better carbon balance (∼75%) than HZSM-5, but the CO 2 yield of γ-Al 2 O 3 was only ∼50%; and there was some desorption of toluene when γ-Al 2 O 3 was used. When a mixture of HZSM-5 and γ-Al 2 O 3 with a mass ratio of 1/2 was used, the carbon balance was up to 90% and 82% of this was CO 2 . The adsorption performance and electric discharge characteristics of the mixed supports were tested in order to rationalize this high CO x yield. After seven cycles of sequential adsorption-plasma oxidation, support and Mn-Ag catalyst deactivation occurred. The support and catalyst were characterized before and after deactivation by SEM, a BET method, XRD, XPS and GC-MS in order to probe the mechanism of their deactivation. 97.6% of the deactivated supports and 76% of the deactivated catalysts could be recovered by O 2 temperature-programmed oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Oxidative dehydrogenation of aqueous ethanol on a carbon supported platinum catalyst

    NARCIS (Netherlands)

    Tillaart, van den J.A.A.; Kuster, B.F.M.; Marin, G.B.M.M.

    1994-01-01

    The kinetics of the selective oxidative dehydrogenation of ethanol to ethanal over a platinum on graphite catalyst with oxygen in water was investigated in a three-phase continuous stirred tank reactor by variation of temp., pH and reactant concns. No effect of the pH on the disappearance rate of

  8. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

    2009-01-01

    The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

  9. Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

    Science.gov (United States)

    Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

    2018-03-06

    We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

  10. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    KAUST Repository

    Zhu, Yihan

    2012-03-19

    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Selective low temperature NH3 oxidation to N2 on copper-based catalysts

    NARCIS (Netherlands)

    Gang, L.; Grondelle, van J.; Anderson, B.G.; Santen, van R.A.

    1999-01-01

    TPD, TPR, UV-visible spectroscopy, and high-resolution electron microscopy (HREM) have been used to characterize the state and reactivity of alumina-supported copper-based catalysts for the oxidation of ammonia to nitrogen. The results of HREM and UV spectra show that a CuAl2O4-like phase is more

  12. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; Sint Annaland, van M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230–260 °C, over a wide range of methanol and oxygen concentrations. The principal

  13. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst

    NARCIS (Netherlands)

    Deshmukh, S.A.R.K.; van Sint Annaland, M.; Kuipers, J.A.M.

    2005-01-01

    The intrinsic steady-state kinetics of the partial oxidation of methanol to formaldehyde over a commercial Fe-Mo catalyst has been studied experimentally in a differentially operated reactor at temperatures of 230¿260 °C, over a wide range of methanol and oxygen concentrations. The principal

  14. Hydrogen peroxide modified Mg-Al-O oxides supported Pt-Sn catalysts for paraffin dehydrogenation

    NARCIS (Netherlands)

    Lai, Y.; He, Songbo; Luo, S.; Bi, W.; Li, XianRu; Sun, Chenglin; Seshan, Kulathuiyer

    2015-01-01

    In this work, a new method to prepare Mg–Al–O oxide by co-precipitation method with addition of H2O2 was developed. The application of Mg–Al–O as a support of Pt–Sn catalysts for paraffin dehydrogenation was investigated. Characterization results indicated that modification of H2O2 (i) enlarged the

  15. Structure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of Alcohols

    OpenAIRE

    Briggs, Daniel Neal

    2010-01-01

    AbstractStructure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of AlcoholsbyDaniel Neal BriggsDoctor of Philosophy in Chemical EngineeringUniversity of California, BerkeleyProfessor Alexis T. Bell, Chair The oxidative carbonylation of alcohols to produce dialkyl carbonates is a process that takes place commercially in a slurry of cuprous chloride in the appropriate alcohol. While this process is chemically efficient, it incurs costs in terms of ene...

  16. Hydrodeoxygenation of vicinal OH groups over heterogeneous rhenium catalyst promoted by palladium and ceria support.

    Science.gov (United States)

    Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Okumura, Kazu; Tomishige, Keiichi

    2015-02-02

    Heterogeneous ReOx-Pd/CeO2 catalyst showed excellent performance for simultaneous hydrodeoxygenation of vicinal OH groups. High yield (>99%), turnover frequency (300 h(-1)), and turnover number (10,000) are achieved in the reaction of 1,4-anhydroerythritol to tetrahydrofuran. This catalyst can be applied to sugar alcohols, and mono-alcohols and diols are obtained in high yields (≥85%) from substrates with even and odd numbers of OH groups, respectively. The high catalytic performance of ReOx-Pd/CeO2 can be assigned to rhenium species with +4 or +5 valence state, and the formation of this species is promoted by H2/Pd and the ceria support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Improved performance of Nb-doped vanadyl pyrophosphate, catalyst for n-butane oxidation to maleic anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Pavarelli, G.; Caldarelli, A.; Cavani, F. [Bologna Univ. (Italy). Dipt. di Chimica Industriale ' Toso Montanari' ; Cortelli, C.; Luciani, S. [Polynt SpA, Scanzorosciate (Italy)

    2013-11-01

    We report here about an investigation on the role of Nb{sup 5+} when used as a promoter for vanadyl pyrophosphate, catalyst for the oxidation of n-butane to maleic anhydride. The effect of Nb was very complex, a function of both its amount and the reaction temperature used. The optimal catalytic behavior was shown for very low Nb contents, i.e., for a V/Nb atomic ratio as low as 150. The main role of Nb was that of accelerating the formation of a limited amount of {gamma}-VOPO{sub 4} on the surface of vanadyl pyrophosphate, by accelerating the oxidation of V{sup 4+} into V{sup 5+} under reaction conditions. (orig.)

  18. Methanol electro-oxidation and direct methanol fuel cell using Pt/Rh and Pt/Ru/Rh alloy catalysts

    International Nuclear Information System (INIS)

    Choi, Jong-Ho; Park, Kyung-Won; Park, In-Su; Nam, Woo-Hyun; Sung, Yung-Eun

    2004-01-01

    Pt-based binary or ternary catalysts containing Rh for use as anodes in direct methanol fuel cells (DMFC) were synthesized by borohydride reduction method combined with freeze-drying. The resulting catalysts had a specific surface area of approximately 65-75 m 2 /g. X-ray diffraction (XRD) patterns indicated that the catalysts were well alloyed and the average size of alloy catalysts was confirmed by transmission electron microscopy (TEM). The Pt/Rh (2:1) and Pt/Ru/Rh (5:4:1) alloy catalysts showed better catalytic activities for methanol electro-oxidation than Pt or Pt/Ru (1:1), respectively

  19. Mechanizm of propylene oxidation on modified cobalt-molybdenum catalysts

    International Nuclear Information System (INIS)

    Kutyrev, M.Yu.; Rozentuller, B.V.; Isaev, O.V.; Margolis, L.Ya.; Krylov, O.V.

    1977-01-01

    Effect is studied of additions of iron, copper, nickel, and vanadium oxides, introduced into cobalt, molybdate, on oxidation reactions of propylene to acrolein and acrylicacid. The principal parameters determining the activity and selectivity of oxidation of propylene and acrolein on modified cobalt molibdate are the structure, the type of Mo-O bond, and the nature of the electron transitions in the solid under the effect of adsorption of the reaction components

  20. Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst : Factors affecting the Rate of Total Oxidation of Ethane and Ethylene

    NARCIS (Netherlands)

    Roos, J.A.; Korf, S.J.; Veehof, R.H.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    Experiments using gas mixtures of O2, C2H6 or C2H4 and CH4 or He have been carried out with a Li/MgO catalyst using a well-mixed reaction system which show that the total oxidation products, CO and CO2, are formed predominantly from ethylene, formed in the oxidative coupling of methane. It is

  1. 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.

  2. Hydrocracking of Cerbera manghas Oil with Co-Ni/HZSM-5 as Double Promoted Catalyst

    Directory of Open Access Journals (Sweden)

    Lenny Marlinda

    2017-05-01

    Full Text Available The effect of various reaction temperature on the hydrocracking of Cerbera manghas oil to produce a paraffin-rich mixture of hydrocarbons with Co-Ni/HZSM-5 as doubled promoted catalyst were studied. The Co-Ni/HZSM-5 catalyst with various metal loading and metal ratio was prepared by incipient wetness impregnation. The catalysts were characterized by XRD, AAS, and N2 adsorption-desorption. Surface area, pore diameter, and pore volume of catalysts decreased with the increasing of metals loading. The hydrocracking process was conducted under hydrogen initial pressure in batch reactor equipped with a mechanical stirrer. The reaction was carried out at a temperature of 300-375 oC for 2 h.  Depending on the experimental condition, the reaction pressure changed between 10 bar and 15 bar.   Several parameters were used to evaluate biofuel produced, including oxygen removal, hydrocarbon composition and gasoline/kerosene/diesel yields. Biofuel was analyzed by Fourier Transform Infrared Spectroscopic (FTIR and gas chromatography-mass spectrometry (GC-MS. The composition of hydrocarbon compounds in liquid products was similar to the compounds in the gasoil sold in unit of Pertamina Gas Stations, namely pentadecane, hexadecane, heptadecane, octadecane, and nonadecane with different amounts for each biofuel produced at different reaction temperatures. However, isoparaffin compounds were not formed at all operating conditions. Pentadecane (n-C15 and heptadecane (n-C17 were the most abundant composition in gasoil when Co-Ni/HZSM-5 catalyst was used. Cerbera Manghas oil can be recommended as the source of non-edible vegetable oil to produce gasoil as an environmentally friendly transportation fuel. Copyright © 2017 BCREC Group. All rights reserved Received: 20th May 2016; Revised: 30th January 2017; Accepted: 10th February 2017 How to Cite: Marlinda, L., Al-Muttaqii, M., Gunardi, I., Roesyadi, A., Prajitno, D.H. (2017. Hydrocracking of Cerbera manghas Oil

  3. Synergistic effect of catalyst for oxidation removal of toluene

    International Nuclear Information System (INIS)

    Zhu Tao; Li Jian; Liang Wenjun; Jin Yuquan

    2009-01-01

    A series of experiments was performed for toluene removal from a gaseous influent at the normal temperature and atmospheric pressure by decomposition due to dielectric barrier discharge generated non-thermal plasma, by using MnO 2 /γ-Al 2 O 3 as catalyst. The removal efficiency of toluene was significantly increased by combining MnO 2 /γ-Al 2 O 3 with NTP. At the same time, the goal of improving energy efficiency and decreasing O 3 from exhaust gas treatment was accomplished.

  4. Synergistic effect of catalyst for oxidation removal of toluene.

    Science.gov (United States)

    Zhu, Tao; Li, Jian; Liang, Wenjun; Jin, Yuquan

    2009-06-15

    A series of experiments was performed for toluene removal from a gaseous influent at the normal temperature and atmospheric pressure by decomposition due to dielectric barrier discharge generated non-thermal plasma, by using MnO(2)/gamma-Al(2)O(3) as catalyst. The removal efficiency of toluene was significantly increased by combining MnO(2)/gamma-Al(2)O(3) with NTP. At the same time, the goal of improving energy efficiency and decreasing O(3) from exhaust gas treatment was accomplished.

  5. Synthesis and Structure Characterization of Phenol-Urea-Formaldehyde Resins in the Presence of Magnesium Oxide as Catalyst

    Directory of Open Access Journals (Sweden)

    Dong-Bin Fan

    2014-08-01

    Full Text Available The objective of this research was to provide a useful approach of polymer synthesis for accelerating the fast cure of phenol-urea-formaldehyde (PUF resin as wood adhesive by optimizing its structure and composition. The PUF resins containing high contents of very reactive groups such as para-methylol groups were synthesized by reacting methylolurea, phenol, and formaldehyde in the presence of magnesium oxide (MgO as catalyst. The effects of synthesis parameters including F/(P + U, OH/P, and MgO/P mole ratios on the structure, composition, curing characteristics, and their relationships of PUF resins were investigated. The results indicated that MgO seemed to be an efficacious catalyst for PUF resin synthesis and promote its faster cure. The increase in the F/(P + U mole ratio or/and OH/P mole ratio appeared to be beneficial for the formation of para-methylol groups and cocondensed methylene linkages between phenolic methylol groups and urea units, and for the removal of unreacted urea. In case of Catalyst/P mole ratio, an appropriate dosage of added metal-ion was very important for synthesizing the high-content reactive groups of PUF resins, otherwise leading to the reverse effects.

  6. One-step flame synthesis of an active Pt/TiO2 catalyst for SO2 oxidation

    DEFF Research Database (Denmark)

    Johannessen, Tue; Koutsopoulos, Sotiris

    2002-01-01

    Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e. a Pt/TiO2 catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average...... size of the platinum particles supported on aggregated nano-particles of TiO2 is approximately 2 nm. The high SO2-oxidation activity of the catalyst proves that platinum is not hidden in the titania matrix. The flame-produced catalyst showed catalytic activity similar to samples prepared by wet...

  7. 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

  8. Why is DsbA such an oxidizing disulfide catalyst?

    DEFF Research Database (Denmark)

    Grauschopf, U; Winther, Jakob R.; Korber, P

    1995-01-01

    in determining the exceptional oxidizing power of DsbA. Mutations that change these two residues can alter the equilibrium oxidation potential of DsbA by more than 1000-fold. A quantitative explanation for the very high redox potential of DsbA was found by measuring the pKa of a single residue, Cys-30. The pKa...

  9. Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

    Science.gov (United States)

    Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

    2017-08-30

    One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

  10. 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

  11. 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.

  12. 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.

  13. Oxidation of methanol to formaldehyde over a series of Fe1-xAlx-V-oxide catalysts

    DEFF Research Database (Denmark)

    Häggblad, Robert; Wagner, Jakob Birkedal; Hansen, Staffan

    2008-01-01

    A series of triclinic Fe1−xAlxVO4 phases with 0x1 were prepared and used in the oxidation of methanol to formaldehyde. The activity measurements revealed that both the activity and especially the selectivity to formaldehyde increased with time of operation for at least 16 h, indicating...... restructuring of the catalysts. Characterisation of the catalysts with XRD, XANES, and electron microscopy after use in methanol oxidation showed that the stability of the bulk phases improved when Al was substituted for Fe in the structure. XRD and XANES of the used FeVO4 showed that it partly transformed...... in methanol oxidation revealed no significant change in the metal composition, in good agreement with the corresponding bulk values, except for a lower Fe value. Steady-state activity data showed a modest increase in specific activity with the Al content, whereas the selectivity to formaldehyde was about 90...

  14. Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

    Science.gov (United States)

    Herz, Richard K.

    1989-01-01

    The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

  15. 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

  16. Photocatalytic oxidation of organic compounds in a hybrid system composed of a molecular catalyst and visible light-absorbing semiconductor.

    Science.gov (United States)

    Zhou, Xu; Li, Fei; Li, Xiaona; Li, Hua; Wang, Yong; Sun, Licheng

    2015-01-14

    Photocatalytic oxidation of organic compounds proceeded efficiently in a hybrid system with ruthenium aqua complexes as catalysts, BiVO4 as a light absorber, [Co(NH3)5Cl](2+) as a sacrificial electron acceptor and water as an oxygen source. The photogenerated holes in the semiconductor are used to oxidize molecular catalysts into the high-valent Ru(IV)=O intermediates for 2e(-) oxidation.

  17. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra; Li, Cheng Chao; Zeng, Hua Chun; Ngiam, Joyce S Y; Seayad, Abdul M.; Chen, Anqi

    2014-01-01

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  18. Kinetic study of the hydration of propylene oxide in the presence of heterogeneous catalyst

    Directory of Open Access Journals (Sweden)

    Akyalcin Sema

    2017-01-01

    Full Text Available The kinetics of the hydration of propylene oxide was studied using a pressurized batch reactor for both uncatalyzed and heterogeneously catalyzed reactions. Lewatit MonoPlus M500/HCO3 - was used as heterogeneous catalyst, which showed better performance than Dowex Marathon A/HCO3 -. The effects of the parameters, namely internal and external diffusion resistances, temperature, catalyst loading and mole ratios of reactants, on the reaction rate were studied. The uncatalyzed and heterogeneously catalyzed reactions were proven to follow a series-parallel irreversible homogeneous mechanism. The temperature dependencies of the rate constants appearing in the rate expressions were determined.

  19. Mesoporous Niobium Oxide Spheres as an Effective Catalyst for the Transamidation of Primary Amides with Amines

    KAUST Repository

    Ghosh, Subhash Chandra

    2014-02-06

    Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds. © 2014 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.

  20. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  1. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  2. Characterization of electro-oxidation catalysts using scanning electrochemical and mass spectral methods

    Science.gov (United States)

    Jambunathan, Krishnakumar

    Low temperature fuel cells have many potential benefits, including high efficiency, high energy density and environmental friendliness. However, logistically appealing fuels for this system, such as reformed hydrocarbons or alcohols, exhibit poor performance because of catalyst poisoning that occurs during oxidation at the anode. This research focuses on the analysis of several model fuels and catalyst materials to understand the impact of catalyst poisoning on reactivity. Two novel experimental tools were developed based upon the local measurement of catalyst performance using scanning, reactivity mapping probes. The Scanning Electrochemical Microscope (SECM) was used to directly measure the rate constant for hydrogen oxidation in the presence and absence of dissolved CO. The Scanning Differential Electrochemical Mass Spectrometer (SDEMS) was exploited to measure the partial and complete oxidation products of methanol and ethanol oxidation. The reactivity of Pt and Pt/Ru catalysts towards the hydrogen oxidation reaction in the absence and presence of adsorbed CO was elucidated using the SECM. Steady state rate constant measurements in the absence of CO showed that the rate of hydrogen oxidation reaction exceeded 1 cms-1 . Steady state rate constant measurements in the presence of CO indicated that the platinum surface is completely inactive due to adsorbed CO. Addition of as little as 6% Ru to the Pt electrode was found to significantly improve the activity of the electrode towards CO removal. SDEMS was used to study the electro-oxidation of methanol on Pt xRuy electrodes at different electrode potentials and temperatures. Screening measurements performed with the SDEMS showed that PtxRu y electrodes containing 6--40% Ru had the highest activity for methanol oxidation. Current efficiencies for CO2 were also calculated under different conditions. SDEMS was also used to study the electro-oxidation of ethanol on Pt xRuy electrodes. The reaction was found to occur

  3. Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

    Science.gov (United States)

    Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

    2014-08-01

    Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Sachdeva, T.O.; Pant, K.K. [Department of Chemical Engineering, Indian Institute of Technology, Delhi, New Delhi, 110016 (India)

    2010-09-15

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO{sub x}) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  5. Deep desulfurization of diesel via peroxide oxidation using phosphotungstic acid as phase transfer catalyst

    International Nuclear Information System (INIS)

    Sachdeva, T.O.; Pant, K.K.

    2010-01-01

    High sulfur level in diesel fuel has been identified as a major contributor to air pollutant in term of sulfur dioxide (SO x ) through diesel fueled vehicles. The main aim of the present work is to develop a promising methodology for ultra deep desulfurization of diesel fuel using oxidation followed by phase transfer of oxidized sulfur. Experiments were carried out in a batch reactor using n-decane as the model diesel compound and also using commercial diesel feedstock. To remove sulfur tetraoctylammonium bromide, phosphotungstic acid, and hydrogen peroxide were used as phase transfer agent, catalyst and oxidant respectively. The percent sulfur removal increases with increasing the initial concentration of sulfur in fuel and with increasing the reaction temperature. Similar trends were observed when commercial diesel was used to carry out desulfurization studies. The amphiphilic catalyst serves as a catalyst and also as an emulsifying agent to stabilize the emulsion droplets. The effects of temperature, agitation speed, quantity of catalyst and the phase transfer agent were studied to estimate the optimal conditions for the reactions. The sulfur removal from a commercial diesel by phase transfer catalysis has been found effective and removal efficiency was more than 98%. Kinetic experiments carried out for the desulfurization revealed that the sulfur removal results are best fitted to a pseudo first order kinetics and the apparent activation energy of desulfurization was 30.6 kJ/mol. (author)

  6. Best combination of promoter and micellar catalyst for the rapid conversion of sorbitol to glucose

    Science.gov (United States)

    Mukherjee, Kakali; Ghosh, Aniruddha; Saha, Rumpa; Sar, Pintu; Malik, Susanta; Saha, Bidyut

    2014-03-01

    Kinetic data for oxidation of D-sorbitol to glucose by hexavalent chromium in aqueous medium and aqueous surfactant medium (SDS, TX-100) have been reported. Effect of promoter such as PA, bipy and phenanthroline on the reaction has been investigated. The reaction is performed under pseudo first order condition with an excess of substrate over the oxidant. The reaction is first order with respect to substrate and oxidant. The micelles have a catalytic effect on the reaction. Combination of phen and TX-100 produces almost twelve times increase in rate of oxidation.

  7. Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

    KAUST Repository

    de Ruiter, J. M.

    2016-09-20

    One of the key challenges in designing light-driven artificial photosynthesis devices is the optimization of the catalytic water oxidation process. For this optimization it is crucial to establish the catalytic mechanism and the intermediates of the catalytic cycle, yet a full description is often difficult to obtain using only experimental data. Here we consider a series of mononuclear ruthenium water oxidation catalysts of the form [Ru(cy)(L)(H2O)](2+) (cy = p-cymene, L = 2,2\\'-bipyridine and its derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques, and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst is investigated using online electrochemical mass spectrometry (OLEMS). The comparison between the calculated absorption spectra of the proposed intermediates with experimental spectra, as well as free energy calculations with electrochemical data, provides strong evidence for the proposed pathway: a water oxidation catalytic cycle involving four proton-coupled electron transfer (PCET) steps. The thermodynamic bottleneck is identified as the third PCET step, which involves O-O bond formation. The good agreement between the optical and thermodynamic data and DFT predictions further confirms the general applicability of this methodology as a powerful tool in the characterization of water oxidation catalysts and for the interpretation of experimental observables.

  8. Revealing the Cytotoxicity of Residues of Phosphazene Catalysts Used for Synthesis of Poly(ethylene oxide)

    KAUST Repository

    Xia, Yening

    2017-08-24

    We herein report a case study on the toxicity of residual catalyst in metal-free polymer. Eight-arm star-like poly(ethylene oxide)s were successfully synthesized via phosphazene-catalyzed ring-opening polymerization of ethylene oxide using sucrose as an octahydroxy initiator. The products were subjected to MTT assay using human cancer cell lines (MDA-MB-231 and A2780). Comparison between the crude and purified products clearly revealed that the residual phosphazenium salts were considerably cytotoxic regardless of the anionic species, and that the cytotoxicity of more bulky t-BuP4 salt was higher than that of t-BuP2 salt. Such results have therefore put forward the necessity for removal of the catalyst residues from PEO-based polymers synthesized through phosphazene catalysis for bio-related applications, and for the development of less or non-toxic organocatalysts for such polymers.

  9. Revealing the Cytotoxicity of Residues of Phosphazene Catalysts Used for Synthesis of Poly(ethylene oxide)

    KAUST Repository

    Xia, Yening; Shen, Jizhou; Alamri, Haleema; Hadjichristidis, Nikolaos; Zhao, Junpeng; Wang, Yucai; Zhang, Guangzhao

    2017-01-01

    We herein report a case study on the toxicity of residual catalyst in metal-free polymer. Eight-arm star-like poly(ethylene oxide)s were successfully synthesized via phosphazene-catalyzed ring-opening polymerization of ethylene oxide using sucrose as an octahydroxy initiator. The products were subjected to MTT assay using human cancer cell lines (MDA-MB-231 and A2780). Comparison between the crude and purified products clearly revealed that the residual phosphazenium salts were considerably cytotoxic regardless of the anionic species, and that the cytotoxicity of more bulky t-BuP4 salt was higher than that of t-BuP2 salt. Such results have therefore put forward the necessity for removal of the catalyst residues from PEO-based polymers synthesized through phosphazene catalysis for bio-related applications, and for the development of less or non-toxic organocatalysts for such polymers.

  10. 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

  11. APPLICATION OF MAGNETIC CATALYSTS TO THE CATALYTIC WET PEROXIDE OXIDATION (CWPO OF INDUSTRIAL WASTEWATER CONTAINING NON BIODEGRADABLE ORGANIC POLLUTANTS

    Directory of Open Access Journals (Sweden)

    Macarena Munoz

    2014-03-01

    Full Text Available A new ferromagnetic -Al2O3-supported iron catalyst has been prepared and its activity and stability have been compared with those of a previous iron-based conventional catalyst and with the traditional homogeneous Fenton process in the oxidation of chlorophenols. The use of solid catalysts improved significantly the efficiency on the use of H2O2, achieving higher mineralization degrees. The magnetic catalyst led to significantly higher oxidation rates than the conventional one due to the presence of both Fe (II and Fe (III. On the other hand, the use of a catalyst with magnetic properties is of interest, since it allows rapid recovery after treatment using a magnetic field. Moreover, it showed a high stability with fairly low iron leaching (<1% upon CWPO runs. An additional clear advantage of this new catalyst is its easy separation and recovery from the reaction medium by applying an external magnetic field.

  12. Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

    Directory of Open Access Journals (Sweden)

    David R. Sellick

    2015-04-01

    Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

  13. OXIDATION OF MERCURY ACROSS SCR CATALYSTS IN COAL-FIRED POWER PLANTS BURNING LOW RANK FUELS

    Energy Technology Data Exchange (ETDEWEB)

    Constance Senior; Temi Linjewile

    2003-07-25

    This is the first Quarterly Technical Report for DOE Cooperative Agreement No: DE-FC26-03NT41728. The objective of this program is to measure the oxidation of mercury in flue gas across SCR catalyst in a coal-fired power plant burning low rank fuels using a slipstream reactor containing multiple commercial catalysts in parallel. The Electric Power Research Institute (EPRI) and Ceramics GmbH are providing co-funding for this program. This program contains multiple tasks and good progress is being made on all fronts. During this quarter, analysis of the coal, ash and mercury speciation data from the first test series was completed. Good agreement was shown between different methods of measuring mercury in the flue gas: Ontario Hydro, semi-continuous emission monitor (SCEM) and coal composition. There was a loss of total mercury across the commercial catalysts, but not across the blank monolith. The blank monolith showed no oxidation. The data from the first test series show the same trend in mercury oxidation as a function of space velocity that has been seen elsewhere. At space velocities in the range of 6,000-7,000 hr{sup -1} the blank monolith did not show any mercury oxidation, with or without ammonia present. Two of the commercial catalysts clearly showed an effect of ammonia. Two other commercial catalysts showed an effect of ammonia, although the error bars for the no-ammonia case are large. A test plan was written for the second test series and is being reviewed.

  14. Catalysts for synthetic liquid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Bruce, L.A.; Turney, T.W.

    1987-12-01

    Fischer-Tropsch catalysts have been designed, characterized and tested for the selective production of hydrocarbons suitable as synthetic liquid transport fuels from synthesis gas (i.e., by the reduction of carbon monoxide with hydrogen). It was found that hydrocarbons in the middle distillate range, or suitable for conversion to that range, could be produced over several of the new catalyst systems. The various catalysts examined included: (1) synthetic cobalt clays, mainly cobalt chlorites; (2) cobalt hydrotalcites; (3) ruthenium metal supported on rare earth oxides of high surface area; and (4) a novel promoted cobalt catalyst. Active and selective catalysts have been obtained, in each category. With the exception of the clays, reproducibility of catalyst performance has been good. Catalysts in groups 2 and 4 have exhibited very high activity, with long lifetimes and easy regeneration.

  15. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Eric I. [Yale Univ., New Haven, CT (United States)

    2015-10-06

    The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractable for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO2 surfaces. Building on this work on anatase, the mechanism by which TiO2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce

  16. Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

    Science.gov (United States)

    Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

    2017-06-01

    This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

  17. Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

    Science.gov (United States)

    Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

    2011-02-01

    We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

  18. Hydrogen Production via Steam Reforming of Ethyl Alcohol over Palladium/Indium Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Tetsuo Umegaki

    2009-01-01

    Full Text Available We report the synergetic effect between palladium and indium oxide on hydrogen production in the steam reforming reaction of ethyl alcohol. The palladium/indium oxide catalyst shows higher hydrogen production rate than indium oxide and palladium. Palladium/indium oxide affords ketonization of ethyl alcohol with negligible by-product carbon monoxide, while indium oxide mainly affords dehydration of ethyl alcohol, and palladium affords decomposition of ethyl alcohol with large amount of by-product carbon monoxide. The catalytic feature of palladium/indium oxide can be ascribed to the formation of palladium-indium intermetallic component during the reaction as confirmed by X-ray diffraction and X-ray photoelectron spectroscopic measurements.

  19. Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium

    Science.gov (United States)

    Abdel Rahim, M. A.; Abdel Hameed, R. M.; Khalil, M. W.

    The use of Ni as a catalyst for the electro-oxidation of methanol in alkaline medium was studied by cyclic voltammetry. It was found that only Ni dispersed on graphite shows a catalytic activity towards methanol oxidation but massive Ni does not. Ni was dispersed on graphite by the electro-deposition from acidic NiSO 4 solution using potentiostatic and galvanostatic techniques. The catalytic activity of the C/Ni electrodes towards methanol oxidation was found to vary with the amount of electro-deposited Ni. The dependence of the oxidation current on methanol concentration and scan rate was discussed. It was concluded from the electro-chemical measurements and SEM analysis that methanol oxidation starts as Ni-oxide is formed on the electrode surface.

  20. PET-modified red mud as catalysts for oxidative desulfurization reactions.

    Science.gov (United States)

    do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

    2017-07-01

    This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Wael Ahmed Abou Taleb Sayed

    2011-01-13

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

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

    Directory of Open Access Journals (Sweden)

    Triyono Triyono

    2010-06-01

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

  3. β-cyclodextrin functionalized on glass micro-particles: A green catalyst for selective oxidation of toluene to benzaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Tahir, M. Nazir, E-mail: tahir.muhammad_nazir@courrier.uqam.ca [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark); Department of Chemistry, University of Quebec at Montreal, QC, H3C 3P8 (Canada); Nielsen, Thorbjørn T.; Larsen, Kim L. [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark)

    2016-12-15

    Highlights: • Functionalization of βCD onto glass micro-particles (GMP-βCD). • Application of GMP-βCD as a green catalyst for the oxidation of toluene. • 82% yield at room temperature. • Repeated use of the catalyst for several cycles. - Abstract: Oxidation of toluene is considered an important process which often requires high temperatures and specific conditions along with heavy-metals based catalysts. In this study, we have developed a green catalyst by functionalizing beta-cyclodextrin onto glass micro-particle surfaces. All surfaces were characterized by X-ray photoelectron spectroscopy and applied to catalyze the selective oxidation of toluene into benzaldehyde (82% yield) at room temperature. The catalyst was stable and could be used repeatedly for several cycles without losing efficiency.

  4. Oxidative dehydrogenation of isobutane over a titanium pyrophosphate catalyst

    Directory of Open Access Journals (Sweden)

    IOAN-CEZAR MARCU

    2005-06-01

    Full Text Available The catalytic properties of titanium pyrophosphate in the oxidative dehydrogenation of isobutane to isobutylene were investigated in the 400 – 550 ºC temperature range. Asignificant change of the product distribution and of the apparent activation energy of the reactionwas observed at about 490 ºC. This phenomenon, already observed in the oxidative dehydrogenation of n-butane, has been interpreted by the existence of two reaction mechanisms depending upon the reaction temperature. Comparison with the n-butane reaction allowed different activation pathways for the activation of alkanes to be proposed. The catalytic properties of TiP2O7 in the oxidative dehydrogenation of isobutane was also compared to those obtained previously with several other pyrophosphates and TiP2O7 was found to be less active and selective for this reaction.

  5. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    Science.gov (United States)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  6. Transesterification of jatropha oil with methanol over Mg–Zn mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    Lee, H.V.; Taufiq-Yap, Y.H.; Hussein, M.Z.; Yunus, R.

    2013-01-01

    A design was developed for the transesterification reaction of non-edible Jatropha Curcas oil using a heterogeneous catalysis system to replace the use of a homogeneous catalytic reaction. Investigations were conducted on solid MgO–ZnO mixed metal oxide catalyst bases with different atomic ratios of magnesium to zinc (Mg/Zn). These catalysts were characterized by BET (Brunauer–Emmer–Teller) surface area analysis, X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS), and the alkalinity of the catalysts was studied by Temperature Programmed Desorption of carbon dioxide (TPD-CO 2 ). The physicochemical properties of the MgO–ZnO binary system were superior to those of the individual bulk oxides of MgO and ZnO. In addition, the formation of a binary system between MgO and ZnO established an effective method for transesterification processes. In this study, the effects of stoichiometric composition and surface characteristics on the transesterification activity of MgO–ZnO were investigated. The catalysts exhibited high catalytic activity (∼80%) with reliable reusability for biodiesel production. -- Highlights: ► Transesterification reaction of non-edible jatropha oil using solid base catalyst. ► MgO–ZnO binary system showed superior effect than the individual MgO and ZnO. ► More than 80% of FAME yield was achieved under mild condition. ► MgO–ZnO catalyst showed reliable reusability throughout 5 runs. ► Fuel properties of prepared biodiesel were complying with the biodiesel standards.

  7. Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

    Science.gov (United States)

    Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

    2012-11-30

    Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Study of ternary-component bismuth molybdate catalysts by 18O2 tracer in the oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Ueda, W.; Moro-oka, Y.; Ikawa, T.

    1981-01-01

    Participation of lattice oxide ions of ternary-component bismuth molybdate catalysts M-Bi-Mo-O (M = Ni, Co, Mg, Mn, Ca, Sr, Ba, and Pb) was investigated using the 18 O 2 tracer in the selective oxidation of propylene to acrolein. The participation of the lattice oxide ions in the oxidation is prominent on every catalyst but the extent of the participation varies significantly depending on the structure of the catalyst. Only lattice oxide ions in the bismuth molybdate phase are incorporated into the oxidized products on the catalysts (M = Ni, Co, Mg, and Mn) where M have smaller ionic radius than Bi 3+ ; catalyst particles are composed of a shell of bismuth molybdates and a core of MMoO 4 . On the other hand, whole oxide ions in the active particles are involved in the oxidation on catalysts having a scheelite-type structure (M = Ca, Sr, Ba, and Pb) where M has a comparable ionic radius to Bi 3+

  9. PdRu/C catalysts for ethanol oxidation in anion-exchange membrane direct ethanol fuel cells

    Science.gov (United States)

    Ma, Liang; He, Hui; Hsu, Andrew; Chen, Rongrong

    2013-11-01

    Carbon supported PdRu catalysts with various Pd:Ru atomic ratios were synthesized by impregnation method, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electrochemical half-cell tests, and the anion-exchange membrane direct ethanol fuel cell (AEM-DEFC) tests. XRD results suggest that the PdRu metal exists on carbon support in an alloy form. TEM study shows that the bimetallic PdRu/C catalysts have slightly smaller average particle size than the single metal Pd/C catalyst. Lower onset potential and peak potential and much higher steady state current for ethanol oxidation in alkaline media were observed on the bimetallic catalysts (PdxRuy/C) than on the Pd/C, while the activity for ethanol oxidation on the pure Ru/C was not noticeable. By using Pd/C anode catalysts and MnO2 cathode catalysts, AEM-DEFCs free from the expensive Pt catalyst were assembled. The AEM DEFC using the bimetallic Pd3Ru/C anode catalyst showed a peak power density as high as 176 mW cm-2 at 80 °C, about 1.8 times higher than that using the single metal Pd/C catalyst. The role of Ru for enhancing the EOR activity of Pd/C catalysts is discussed.

  10. Chromium–tungsten–titanium mixed oxides solid catalyst for fatty acid methyl ester synthesis from palm fatty acid distillate

    International Nuclear Information System (INIS)

    Wan, Zuraida; Hameed, B.H.

    2014-01-01

    Highlights: • Chromium–tungsten–titanium mixed oxides as solid catalyst. • Catalyst used for esterification of palm fatty acid distillate to methyl esters. • The maximum methyl ester content is 83%. • Catalyst has shown good activity and can be recycled for 4 times. - Abstract: Chromium–tungsten–titanium mixed oxides solid catalysts were prepared and evaluated in the esterification of palm fatty acid distillate (PFAD) to produce fatty acid methyl ester (FAME). Esterification was conducted in a batch reactor at 110–200 °C temperature ranges. The catalysts were characterized by several techniques such as BET, TEM, FTIR, TGA, XRD, EDX and SEM. The treatment conditions during catalyst preparation, effect of reaction parameters, leaching of the active species and the recycled use of the catalyst were investigated. The catalyst with formula CrWTiO 2 was found to be the most active with maximum FAME content of 83% obtained at best reaction conditions of 170 °C for 3 h, 2:1 (methanol to oil molar ratio) and 2 wt.% catalyst dosage. The catalyst can be recycled for 4 times. The results revealed CrWTiO 2 good potentials for use in esterification of high acid value oil

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

    Science.gov (United States)

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

    2007-07-01

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

  12. Core-shell rhodium sulfide catalyst for hydrogen evolution reaction / hydrogen oxidation reaction in hydrogen-bromine reversible fuel cell

    Science.gov (United States)

    Li, Yuanchao; Nguyen, Trung Van

    2018-04-01

    Synthesis and characterization of high electrochemical active surface area (ECSA) core-shell RhxSy catalysts for hydrogen evolution oxidation (HER)/hydrogen oxidation reaction (HOR) in H2-Br2 fuel cell are discussed. Catalysts with RhxSy as shell and different percentages (5%, 10%, and 20%) of platinum on carbon as core materials are synthesized. Cyclic voltammetry is used to evaluate the Pt-equivalent mass specific ECSA and durability of these catalysts. Transmission electron microscopy (TEM), X-ray Photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX) techniques are utilized to characterize the bulk and surface compositions and to confirm the core-shell structure of the catalysts, respectively. Cycling test and polarization curve measurements in the H2-Br2 fuel cell are used to assess the catalyst stability and performance in a fuel cell. The results show that the catalysts with core-shell structure have higher mass specific ECSA (50 m2 gm-Rh-1) compared to a commercial catalyst (RhxSy/C catalyst from BASF, 6.9 m2 gm-Rh-1). It also shows better HOR/HER performance in the fuel cell. Compared to the platinum catalyst, the core-shell catalysts show more stable performance in the fuel cell cycling test.

  13. High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

    International Nuclear Information System (INIS)

    Ma Liang; Liu Changpeng; Liao Jianhui; Lu Tianhong; Xing Wei; Zhang Jiujun

    2009-01-01

    A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH 4 ) 2 PtCl 6 and Ru(OH) 3 ) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru 0 ) and hydrous ruthenium oxides (RuO x H y ) species on the catalyst surface. However, RuO x H y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO 2 ) species on the catalyst surface was found to be less active.

  14. Designing Multifunctionality into Single Phase and Multiphase Metal-Oxide-Selective Propylene Ammoxidation Catalysts

    Directory of Open Access Journals (Sweden)

    James F. Brazdil

    2018-03-01

    Full Text Available Multifunctionality is the hallmark of most modern commercial heterogeneous catalyst systems in use today, including those used for the selective ammoxidation of propylene to acrylonitrile. It is the quintessential principle underlying commercial catalyst design efforts since petrochemical process development is invariably driven by the need to reduce manufacturing costs. This is in large part achieved through new and improved catalysts that increase selectivity and productivity. In addition, the future feedstocks for chemical processes will be invariably more refractory than those currently in use (e.g., replacing alkenes with alkanes or using CO2, thus requiring a disparate combination of chemical functions in order to effect multiple chemical transformations with the fewest separate process steps. This review summarizes the key chemical phenomena behind achieving the successful integration of multiple functions into a mixed-metal-oxide-selective ammoxidation catalyst. An experiential and functional catalyst design model is presented that consists of one or both of the following components: (1 a mixed-metal-oxide–solid solution where the individual metal components serve separate and necessary functions in the reaction mechanism through their atomic level interaction in the context of a single crystallographic structure; (2 the required elemental components and their catalytic function existing in separate phases, where these phases are able to interact for the purposes of electron and lattice oxygen transfer through the formation of a structurally coherent interface (i.e., epitaxy between the separate crystal structures. Examples are provided from the literature and explained in the context of this catalyst design model. The extension of the model concepts to the design of heterogeneous catalysts in general is also discussed.

  15. SnO2 promoted by alkali metal oxides for soot combustion: The effects of surface oxygen mobility and abundance on the activity

    Science.gov (United States)

    Rao, Cheng; Shen, Jiating; Wang, Fumin; Peng, Honggen; Xu, Xianglan; Zhan, Hangping; Fang, Xiuzhong; Liu, Jianjun; Liu, Wenming; Wang, Xiang

    2018-03-01

    In this study, SnO2-based catalysts promoted by different alkali metal oxides with a Sn/M (M = Li, Na, K, Cs) molar ratio of 9/1 have been prepared for soot combustion. In comparison with the un-modified SnO2 support, the activity of the modified catalysts has been evidently enhanced, following the sequence of CsSn1-9 > KSn1-9 > NaSn1-9 > LiSn1-9 > SnO2. As testified by Raman, H2-TPR, soot-TPR-MS, XPS and O2-TPD results, the incorporation of various alkali metal oxides can induce the formation of more abundant and mobile oxygen species on the surface of the catalysts. Moreover, quantified results have proved that the amount of the surface active oxygen species is nearly proportional to the activity of the catalysts. CsSn1-9, the catalyst promoted by cesium oxide, owns the largest amount of surface mobile oxygen species, thus having the highest activity among all the studied catalysts. It is concluded that the amount of surface active and mobile oxygen species is the major factor determining the activity of the catalysts for soot combustion.

  16. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  17. NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

    2016-04-18

    The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  18. 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)

  19. Facial synthesis of porous hematite supported Pt catalyst and its photo enhanced electrocatalytic ethanol oxidation performance

    International Nuclear Information System (INIS)

    Kang, Shuai; Shen, Pei Kang

    2015-01-01

    Graphical Abstract: A porous α-Fe 2 O 3 supported Pt catalyst has been synthesized by a facial thermal treatment assisted precipitation method and the materials show a illumination enhanced performance for ethanol oxidation. Display Omitted -- Highlights: •A porous α-Fe 2 O 3 supported Pt catalyst has been synthesized for the first time. •With the addition of α-Fe 2 O 3 , the current density of Pt/C grows about 51% under illumination and 32% in the dark compared with unsupported catalyst. •The current increases under illuminationin chronoamperometric experiments at a given potential of 0.7 V due to the photons from light provide energy for CO stripping. •This work demostrates an optical strategy to accelerate electrode reactions towards ethanol oxidation reaction. -- Abstract: The porous α-Fe 2 O 3 supported Pt catalyst is synthesized by a facial thermal treatment assisted precipitation method. The particle size of Pt is less than 3 nm. The pore diameters of α-Fe 2 O 3 particles are concentrated to 2.46 nm in a mesooporous scale. Its electrochemical performance is tested. The ethanol oxidation current of the Pt/Fe 2 O 3 catalsyt obviously improves under illumination, compared with that in the dark, during the optical switching operation. Moreover, with the addition of α-Fe 2 O 3 , the ethanol oxidation current of Pt/C grows about 51% under illumination and 32% in the dark; the onset potential shifts negtively for about 20 mV. This work demostrates an optical strategy which can be a potential alternative to accelerate electrode reactions towards ethanol oxidation reaction

  20. Transition metal oxide loaded MCM catalysts for photocatalytic ...

    Indian Academy of Sciences (India)

    Transition metal oxide (TiO2, Fe2O3, CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step .... washed consecutively with water and ethanol, and cal- cined at 823 K for 5 .... conversion was observed in 1 h when the reaction was.

  1. Supported transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing

    International Nuclear Information System (INIS)

    Ho, T.C.; Chianelli, R.R.; Jacobson, A.J.; Young, A.R.

    1987-01-01

    A process is described for hydrotreating a hydrocarbon feed which comprises contacting the feed at a temperature of at least about 150 0 C and heating the composite at elevated temperature of at least about 150 0 C, in the presence of sulfur and under oxygen-free conditions for a time sufficient to form the catalyst. The precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals which are chelated by at least one neutral, nitrogen-containing polydentate ligand L. The divalent promoter metal is selected from the group consisting of Ni, Co, Zn, Cu and mixture thereof. The contacting occurs for a time sufficient to hydrotreat at least a portion of the feed

  2. Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: Efficient routes to acetic acid and ethyl acetate

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Christiansen, Sofie Egholm; Thomsen, M.L.D.

    2007-01-01

    The aerobic oxidation of aqueous ethanol to produce acetic acid and ethyl acetate was studied using heterogeneous gold catalysts. Comparing the performance of Au/MgAl2O4 and Au/TiO2 showed that these two catalysts exhibited similar performance in the reaction. By proper selection of the reaction...

  3. Oxidative Dehydrogenation of n-​Butane: Activity and Kinetics Over VOx​/Al2O3 Catalysts

    NARCIS (Netherlands)

    Madaan, N.; Haufe, R.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    The catalytic activity of a VOx/Al2O3 catalyst for the oxidative dehydrogenation of n-​butane is investigated. The effects of reaction temp., oxygen to n-​butane ratio and GHSV on the catalytic performance are examd. and optimized. Interestingly, this simple catalyst gives good conversion and

  4. Insight into the Effect of Sn on CO and Formic Acid Oxidation at PtSn Catalysts

    DEFF Research Database (Denmark)

    Stevanović, S.; Tripković, D.; Tripkovic, Vladimir

    2014-01-01

    The role of Sn on the catalytic activity for CO and formic acid oxidation is studied by comparing the activities of differently treated PtSn/C and Pt/C catalysts. The catalysts are prepared by a microwave-assisted polyol synthesis method. As revealed by scanning tunneling and transmission electron...

  5. The oxidative dehydrogenation of methanol to formaldehyde over silver catalysts in relation to the oxygen-silver interaction

    NARCIS (Netherlands)

    Lefferts, Leonardus; van Ommen, J.G.; Ross, J.R.H.

    1986-01-01

    The properties of silver in the oxidative dehydrogenation of methanol were studied in a flow reactor under near industrial conditions. The influences of temperature, concentration of both reactants, gas velocity, space velocity, the form of the silver catalyst and surface composition of the catalyst

  6. KF-loaded mesoporous Mg-Fe bi-metal oxides: high performance transesterification catalysts for biodiesel production.

    Science.gov (United States)

    Tao, Guiju; Hua, Zile; Gao, Zhe; Zhu, Yan; Zhu, Yan; Chen, Yu; Shu, Zhu; Zhang, Lingxia; Shi, Jianlin

    2013-09-21

    Using newly developed mesoporous Mg-Fe bi-metal oxides as supports, a novel kind of high performance transesterification catalysts for biodiesel production has been synthesized. More importantly, the impregnation solvent was for the first time found to substantially affect the structures and catalytic performances of the resultant transesterification catalysts.

  7. Impact of potassium promoter on Cu–Fe based mixed alcohols synthesis catalyst

    International Nuclear Information System (INIS)

    Ding, Mingyue; Tu, Junling; Qiu, Minghuang; Wang, Tiejun; Ma, Longlong; Li, Yuping

    2015-01-01

    Highlights: • Adding K facilitated the immigration of bulky iron species to surface layers. • Adding potassium strengthened the interaction of Fe–K on the surface layers. • Increasing K content facilitated the formation of C 2 + OH. • A maximum in catalytic activity is obtained at 0.5 wt.% of potassium loading. - Abstract: Impacts of K promoter on microstructures of a precipitated Cu–Fe based catalyst were studied by N 2 -physisorption (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD) and hydrogen temperature-programmed desorption/reduction (H 2 -TPD/TPR). Mixed alcohols synthesis (MAS) was carried out in a fixed-bed reactor. The results indicated that incorporation of K in the Cu–Fe based catalyst decreased the surface area of the particles, whereas promoted the immigration of bulky iron species to surface layers and strengthened the interaction of surface Fe–Cu. The increase of K concentration weakened the H 2 chemisorption and restrained the reduction of both the Cu and Fe species. The catalytic activity and mixed alcohols selectivity increased accompanied with a gradually increasing K concentration, and reached the highest values as the amount of K increased to 0.5 wt.%. Subsequently, the MAS activity and selectivity C 2 + OH presented a decreasing trend. In addition, the increase of K concentration facilitated the formation of heavy hydrocarbons

  8. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Gao, Ruimin [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Wang, Junlong [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China)

    2015-05-15

    M{sub 2}(PcAN){sub 2} (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M{sub 2}(PcAN){sub 2}–W-HZSM-5) or the M{sub 2}(PcTN){sub 2} doping W-HZSM-5 (M{sub 2}(PcTN){sub 2}/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 and Cu{sub 2}(PcTN){sub 2}/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu{sub 2}(PcTN){sub 2}/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N{sub 2} adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed.

  9. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    International Nuclear Information System (INIS)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

    2015-01-01

    M 2 (PcAN) 2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M 2 (PcAN) 2 –W-HZSM-5) or the M 2 (PcTN) 2 doping W-HZSM-5 (M 2 (PcTN) 2 /W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu 2 (PcAN) 2 –W-HZSM-5 and Cu 2 (PcTN) 2 /W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu 2 (PcTN) 2 /W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N 2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu 2 (PcAN) 2 –W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed

  10. Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

    Science.gov (United States)

    Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

    2018-01-01

    Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

  11. Synthesis, Characterization, and Use of Novel Bimetal Oxide Catalyst for Photoassisted Degradation of Malachite Green Dye

    Directory of Open Access Journals (Sweden)

    K. L. Ameta

    2014-01-01

    Full Text Available This work reports a simple, novel, and cost effective synthesis of nanobimetal oxide catalyst using cerium and cadmium nitrates as metal precursors. The cerium-cadmium oxide nanophotocatalyst was synthesized by coprecipitation method and characterized by X-ray powder diffraction method to analyze the particle size. XRD study reveals a high degree of crystallinity and 28.43 nm particle size. The photocatalytic efficiency of the synthesized nanobimetal catalyst was examined by using it for the photocatalytic degradation of malachite green dye. Experiments were conducted to study the effect of various parameters, such as the pH of the dye solution, concentration of dye, amount of catalyst, and light intensity on the rate of dye degradation. The progress of the dye degradation was monitored spectrophotometrically by taking the optical density of the dye solution at regular intervals. Experimental results indicate that the dye degrades best at pH 8.0 with light intensity 600 Wm−2 and catalyst loading 0.03 g/50 mL of dye solution. The rate constant for the reaction was 7.67 × 10−4 s−1.

  12. Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

    Energy Technology Data Exchange (ETDEWEB)

    Mondal, Arijit; Mukherjee, Debkumar, E-mail: debkumarmukherjee@rediffmail.com [Ramsaday College, Department of Chemistry (India); Adhikary, Bibhutosh, E-mail: adhikarybibhu@yahoo.com [Indian Institute of Engineering, Sciences and Technology, Shibpur, Department of Chemistry (India); Ahmed, Md Azharuddin [University of Calcutta, Department of Physics (India)

    2016-05-15

    Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4–6 nm) can also be prepared from PdCl{sub 2} and K{sub 2}PtCl{sub 4}, respectively, using the same surfactant but require high temperature (~120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90–95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.Graphical Abstract.

  13. Morphological Effect of Pd Catalyst on Ethanol Electro-Oxidation Reaction

    Directory of Open Access Journals (Sweden)

    Rosalba Fuentes Ramírez

    2012-09-01

    Full Text Available In the present study, three different structures with preferentially exposed crystal faces were supported on commercial carbon black by the polyol method (nanoparticles (NP/C, nanobars (NB/C and nanorods (NR/C. The electrocatalysts were characterized by XRD, TEM, TGA and cyclic voltammetry at three different ethanol concentrations. Considerable differences were found in terms of catalytic electroactivity. At all ethanol concentrations, the trend observed for the ethanol oxidation peak potential was preserved as follows: NB/C < NP/C< NR/C < commercial Pd/C. This result indicates that, from a thermodynamics point of view, the NB/C catalyst enclosed by Pd(100 facets presented the highest activity with respect to ethanol electro-oxidation among all of the catalysts studied.

  14. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo [EcoTopia Science Institute (Japan); Hirabayashi, Daisuke; Enokida, Youichi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)

    2013-07-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U{sub 3}O{sub 8} without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  15. Oxidative desulfurization of benzothiophene and thiophene with WO{sub x}/ZrO{sub 2} catalysts: Effect of calcination temperature of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, Zubair; Jeon, Jaewoo [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Oxidative desulfurization was studied with WO{sub x}/ZrO{sub 2} calcined at different temp. Black-Right-Pointing-Pointer The importance of the phases of zirconia and tungsten oxide was suggested. Black-Right-Pointing-Pointer The catalyst was analyzed thoroughly with Raman and XRD techniques. Black-Right-Pointing-Pointer The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO{sub x}/ZrO{sub 2} catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO{sub x}/ZrO{sub 2} catalyst is around 700 Degree-Sign C. The most active catalyst is composed of tetragonal zirconia (ZrO{sub 2}) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO{sub 3} and monoclinic ZrO{sub 2} for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO{sub x}/ZrO{sub 2} catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

  16. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis

    Directory of Open Access Journals (Sweden)

    Ali Abbasi

    2014-03-01

    Full Text Available Iron-Cobalt catalyst is well known from both operational and economical aspects for Fischer-Tropsch synthesis. Effort to increase the efficiency of this kind of catalyst is an important research topic. In this work, the effect of lanthanum on characteristic behavior, conversion and selectivity of a Fe-Co/SiO2 Fischer-Tropsch catalyst was studied. The Fe-Co-La/SiO2 Catalysts were prepared using an incipient wetness impregnation method. These catalysts were then characterized by XRF-EDAX, BET and TPR techniques, and their performance were evaluated in a lab-scale reactor at 250ºC, H2/CO = 1.8 of molar ratio, 16 barg pressure and GHSV=600 h-1. TPR analysis showed that the addition of La lowered the reduction temperature of Fe-Co catalyst, and due to a lower temperature, the sintering of the catalyst can be mitigated. Furthermore, from the micro reactor tests (about 4 days, it was found that lanthanum promoted catalyst had higher selectivity toward hydrocarbons, and lower selectivity toward CO2.Received: 8th July 2013; Revised: 18th November 2013; Accepted: 1st December 2013[How to Cite: Abbasi, A., Ghasemi, M., Sadighi, S. (2014. Effect of Lanthanum as a Promoter on Fe-Co/SiO2 Catalyst for Fischer-Tropsch Synthesis. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1: 23-27. (doi:10.9767/bcrec.9.1.5142.23-27][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5142.23-27

  17. Research of catalysts for isotope enrichment of deuterium oxide in water - PX15-03/90 progress report

    International Nuclear Information System (INIS)

    1990-10-01

    The operation results of pre-concentration stages from the Pilot Unity, and the technical information important to the project of development of catalyst for isotope concentration of deuterium oxides (D 2 O) are described. (C.G.C.)

  18. Mesoporous Silica Supported Au Nanoparticles with Controlled Size as Efficient Heterogeneous Catalyst for Aerobic Oxidation of Alcohols

    Directory of Open Access Journals (Sweden)

    Xuefeng Chu

    2015-01-01

    Full Text Available A series of Au catalysts with different sizes were synthesized and employed on amine group functionalized ordered mesoporous silica solid supports as catalyst for the aerobic oxidation of various alcohols. The mesoporous silica of MCM-41 supported Au nanoparticles (Au-1 exhibited the smallest particle size at ~1.8 nm with superior catalytic activities owing to the confinement effect of the mesoporous channels. Au-1 catalyst is also very stable and reusable under aerobic condition. Therefore, this presented work would obviously provide us a platform for synthesizing more size-controlled metal catalysts to improve the catalytic performances.

  19. Preparation of Cyclic Urethanes from Amino Alcohols and Carbon Dioxide Using Ionic Liquid Catalysts with Alkali Metal Promoters

    OpenAIRE

    Masahiko Arai; Hisanori Senboku; Hiroshi Kanamaru; Shin-ichiro Fujita

    2006-01-01

    Several ionic liquids were applied as catalysts for the synthesis of cyclic urethanes from amino alcohols and pressurized CO2 in the presence of alkali metal compounds as promoters. A comparative study was made for the catalytic performance using different ionic liquids, substrates, promoters, and pressures. The optimum catalytic system was BMIM-Br promoted by K2CO3, which, for 1-amino-2-propanol, produced cyclic urethane in 40% yield with a smaller yield of substituted cyclic ...

  20. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  1. Nature of the activates places of the acid solid catalysts of the sulphated metallic oxides type

    International Nuclear Information System (INIS)

    Gomez, Miguel A; Fontalvo Javier

    1998-01-01

    In this revision the state of the knowledge is presented with respect to the understanding of the nature of the active places for the strongly acid solid catalysts of the type sulphated metallic oxides. The results presented by means of models are based on the characterization of the properties physicochemical carried out by means of technical as XPS, to GO, NMR etc., and the evaluation of the catalytic activity in different applications

  2. Trickle bed reactor for the oxidation of phenol over active carbon catalyst

    OpenAIRE

    Gabbiye, Nigus; Font Capafons, Josep; Fortuny Sanromá, Agustín; Bengoa, Christophe José; Fabregat Llangotera, Azael; Stüber, Frank Erich

    2009-01-01

    The catalytic wet air oxidation of phenol using activated carbon has been performed in a laboratory trickle bed reactor over a wide range of operating variables (PO2, T, FL and Cph,o) and hydrodynamic conditions. The influence of different start-up procedures (saturation of activated carbon) has also been tested. Further improvement of activity and stability has been checked for by using dynamic TBR operation concept or impregnated Fe/carbon catalyst. The results obtained confi...

  3. Supported Co-Mn-Al Mixed Oxides as Catalysts for N2O Decomposition.

    Czech Academy of Sciences Publication Activity Database

    Pacultová, K.; Karásková, C.; Strakošová, J.; Jirátová, Květa; Obalová, L.

    2015-01-01

    Roč. 18, č. 20 (2015), s. 1114-1122 ISSN 1631-0748. [AWPAC2014 - International Symposium on Air & Water Pollution Abatement Catalysis. Krakow, 01.09.2014-05.09.2014] R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : supported catalysts * heterogeneous catalysis * spinel phase * nitrogen oxides Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.798, year: 2015

  4. Effect of iron promoter on structure and performance of CuMnZnO catalyst for higher alcohols synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Mingyue [Key Laboratory of Renewable Energy and Natural Gas Hydrate, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Guangzhou Institute of Energy Conversion, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Qiu, Minghuang [Key Laboratory of Renewable Energy and Natural Gas Hydrate, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Guangzhou Institute of Energy Conversion, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Graduate School of Chinese Academy of Science, Beijing 100049 (China); Wang, Tiejun [Key Laboratory of Renewable Energy and Natural Gas Hydrate, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Guangzhou Institute of Energy Conversion, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Ma, Longlong; Wu, Chuangzhi [Key Laboratory of Renewable Energy and Natural Gas Hydrate, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Guangzhou Institute of Energy Conversion, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Liu, Jianguo [Key Laboratory of Renewable Energy and Natural Gas Hydrate, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Guangzhou Institute of Energy Conversion, Chinese Academy of Science, Guangzhou Guangdong 510640 (China); Graduate School of Chinese Academy of Science, Beijing 100049 (China)

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer Incorporation of iron promotes the dispersion of catalyst particles. Black-Right-Pointing-Pointer Adding iron facilitates the separation of CuO from the Cu-Mn solid solution. Black-Right-Pointing-Pointer Both the copper and iron carbides are well dispersed in higher iron amount. Black-Right-Pointing-Pointer The selectivity to C{sub 2}{sup +}OH is promoted by increasing iron concentration. -- Abstract: Effect of iron promoter on the microstructures of CuMnZnO catalysts was investigated by N{sub 2} physical adsorption (BET), X-ray diffraction (XRD), and temperature-programmed reduction of hydrogen (H{sub 2}-TPR). Higher alcohols synthesis (HAS) was performed in a fixed bed reactor. The characterization results indicated that incorporation of iron in the CuMnZnO catalyst resulted in the increase of BET surface area and the dispersion of catalyst particles. Adding iron facilitated the formation of Fe-Mn solid solution and reduced the interaction between copper and manganese, which promoted the separation of CuO from the Cu-Mn solid solution and the reduction of the catalyst. In the HAS reaction, the catalytic activity of CO hydrogenation and the selectivity to C{sub 2}{sup +}OH and hydrocarbons presented an increasing trend with the increase in iron concentration, which may be attributed to the synergistic effect between the dispersed copper and iron carbides.

  5. CO2 methanation on the catalyst of Ni/MCM-41 promoted with CeO2.

    Science.gov (United States)

    Wang, Xiaoliu; Zhu, Lingjun; Liu, Yincong; Wang, Shurong

    2018-06-01

    CO 2 as a raw feed combined with renewable hydrogen for the production of useful chemicals and alternative energy products is one of the solutions to environmental and energy problems. In this study, a series of Ni-xCeO 2 /MCM-41 catalysts with a nickel content of 20wt% were prepared through deposition precipitation method for CO 2 methanation. Different characterization methods, including BET, XRD, TEM, SEM, H 2 -TPR and H 2 -TPD were applied to help explore the influence mechanism of CeO 2 on Ni/MCM-41 in CO 2 methanation. It was found that all CeO 2 -promoted catalysts exhibited enhanced catalytic activity when compared to Ni/MCM-41. The catalyst modified with 20wt% CeO 2 showed the best catalytic performance, with CO 2 conversion and CH 4 selectivity of 85.6% and 99.8%, respectively, at the temperature of 380°C under atmospheric pressure. The synergetic effects among Ni 0 active sites, the promoter and the support, including nickel dispersion improvement and increased CO 2 adsorption sites due to the addition of CeO 2 , were considered as important factors for high reactivity of the promoted catalysts. The stability test showed that the promoted catalyst maintained its high reactivity after 30h. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Heterogeneous catalysis in the liquid-phase oxidation of olefins--3. The activity of supported vanadium-chromium binary oxide catalyst for the oxidation of cyclohexene

    Energy Technology Data Exchange (ETDEWEB)

    Takehira, K; Hayakawa, T; Ishikawa, T

    1979-03-01

    The activity of supported vanadium-chromium binary oxide catalyst for the oxidation of cyclohexene to 1-cyclohexenyl hydroperoxide, 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was due to the interaction between the metal oxides and the carriers. The oxidation reaction was carried out in benzene at 60/sup 0/C for four hours with the binary oxide supported on (GAMMA)-alumina or silica; three series of catalysts were prepared by combining the vanadium and chromium oxide components with alumina hydrate or silica sol by a kneading method. The silica-supported catalysts had the greatest activity, the highest being the V/sub 2/O/sub 5//SiO/sub 2/ system, which lost its activity quickly during the reaction. This was followed in activity by the Cr/sub 2/O/sub 3//SiO/sub 2/ system, containing the chromium(V) species. The Cr/sub 2/O/sub 3//Al/sub 2/O/sub 3/ system also had high activity and the chromium(V) species. The vanadium and chromium metal ions are probably coordinated tetrahedrally on the support, and these complexes catalyze cyclohexene autoxidation by decomposing 1-cyclohexenyl hydroperoxide.

  7. Enhanced methanol electro-oxidation reaction on Pt-CoO{sub x}/MWCNTs hybrid electro-catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Nouralishahi, Amideddin, E-mail: Nouralishahi@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Caspian Faculty of Engineering, University of Tehran, P.O. Box 43841-119, Rezvanshahr (Iran, Islamic Republic of); Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Rashidi, Ali Morad, E-mail: Rashidiam@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: Mortazav@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Khodadadi, Abbas Ali, E-mail: Khodadad@ut.ac.ir [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, P.O. Box 11155/4563, Tehran (Iran, Islamic Republic of); Choolaei, Mohammadmehdi, E-mail: Choolaeimm@ripi.ir [Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran (Iran, Islamic Republic of)

    2015-04-30

    Highlights: • Promoting effects of Cobalt oxide on methanol electro-oxidation over Pt/MWCNTs are investigated. • Higher activity, about 2.9 times, and enhanced stability are observed on Pt-CoO{sub x}/MWCNTs. • Electrochemical active surface area of Pt nanoparticles is significantly improved upon CoO{sub x} addition. • Bi-functional mechanism is facilitated in presence of CoO{sub x}. - Abstract: The electro-catalytic behavior of Pt-CoO{sub x}/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH{sub 4} as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoO{sub x}, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of CO{sub ads} on Pt active sites by the participation of CoO{sub x}. Compared to Pt/MWCNTs, Pt-CoO{sub x}/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoO{sub x}/MWCNTs, at small overpotentials. However, at higher overpotentials, the

  8. Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst

    Directory of Open Access Journals (Sweden)

    Luqman Buchori

    2017-05-01

    Full Text Available Biodiesel synthesis through transesterification of soybean oil with methanol on hybrid catalytic-plasma reactor over sulphated zinc oxide (SO42-/ZnO active acid catalyst was investigated. This research was aimed to study effects of Weight Hourly Space Velocity (WHSV and the catalyst diameter on performance of the hybrid catalytic-plasma reactor for biodiesel synthesis. The amount (20.2 g of active sulphated zinc oxide solid acid catalysts was loaded into discharge zone of the reactor. The WHSV and the catalyst diameter were varied between 0.89 to 1.55 min-1 and 3, 5, and 7 mm, respectively. The molar ratio of methanol to oil as reactants of 15:1 is fed to the reactor, while operating condition of the reactor was kept at reaction temperature of 65 oC and ambient pressure. The fatty acid methyl ester (FAME component in biodiesel product was identified by Gas Chromatography - Mass Spectrometry (GC-MS. The results showed that the FAME yield decreases with increasing WHSV. It was found that the optimum FAME yield was achieved of 56.91 % at WHSV of 0.89 min-1 and catalyst diameter of 5 mm and reaction time of 1.25 min. It can be concluded that the biodiesel synthesis using the hybrid catalytic-plasma reactor system exhibited promising the FAME yield. Copyright © 2017 BCREC Group. All rights reserved Received: 15th November 2016; Revised: 24th December 2016; Accepted: 16th February 2017 How to Cite: Buchori, L., Istadi, I., Purwanto, P. (2017. Effects of Weight Hourly Space Velocity and Catalyst Diameter on Performance of Hybrid Catalytic-Plasma Reactor for Biodiesel Synthesis over Sulphated Zinc Oxide Acid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 227-234 (doi:10.9767/bcrec.12.2.775.227-234 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.775.227-234

  9. Aerobic Oxidation of Xylose to Xylaric acid in Water over Pt Catalysts.

    Science.gov (United States)

    Saha, Basudeb; Sadula, Sunitha

    2018-05-02

    Energy-efficient catalytic conversion of biomass intermediates to functional chemicals can enable bio-products viable. Herein, we report an efficient and low temperature aerobic oxidation of xylose to xylaric acid, a promising bio-based chemical for the production of glutaric acid, over commercial catalysts in water. Among several heterogeneous catalysts investigated, Pt/C exhibits the best activity. Systematic variation of reaction parameters in the pH range of 2.5 to 10 suggests that the reaction is fast at higher temperatures but high C-C scission of intermediate C5-oxidized products to low carbon carboxylic acids undermines xylaric acid selectivity. The C-C cleavage is also high in basic solution. The oxidation at neutral pH and 60 C achieves the highest xylaric acid yield (64%). O2 pressure and Pt-amount have significant influence on the reactivity. Decarboxylation of short chain carboxylic acids results in formation of CO2, causing some carbon loss; however such decarboxylation is slow in the presence of xylose. The catalyst retained comparable activity, in terms of product selectivity, after five cycles with no sign of Pt leaching. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Jianghua; Wang, Guanghui; Zeng, Danlin; Tang, Yan [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Wang, Meng; Li, Yanjun [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

    2009-12-15

    Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]{sub 2} in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly. (author)

  11. A New Design Strategy for Observing Lithium Oxide Growth-Evolution Interactions Using Geometric Catalyst Positioning.

    Science.gov (United States)

    Ryu, Won-Hee; Gittleson, Forrest S; Li, Jinyang; Tong, Xiao; Taylor, André D

    2016-08-10

    Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O2 cells by characterizing products that grow from the electrode surface. Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. The influence of the catalyst position on product composition is further verified by ex situ X-ray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  13. USE OF CARBON CATALYSTS FOR OXIDATIVE DESTRUCTION OF WASTEWATERS

    Directory of Open Access Journals (Sweden)

    Svetlana S. Stavitskaya

    2007-06-01

    Full Text Available The paper considers a possibility of using the catalytic action of the carbonaceous adsorbents modified by different ways for the purification of various solutions, natural and wastewaters. It has been found that the oxidative destruction of organic (phenols, dyes, pesticides, etc. and inorganic (H2S contaminants in water solutions is considerably intensified in the presence of both ordinary activated carbons and especially, carbons with specially introduced catalytic additives. It is shown that the sewage treatment level is strongly affected by the amount and nature of a modifying agent introduced on the carbon surface.

  14. Cyclodextrin ketones as oxidation catalysts: investigation of bridged derivatives

    DEFF Research Database (Denmark)

    Fenger, Thomas Hauch; Marinescu, Lavinia; Bols, Mikael

    2009-01-01

    A series of alpha-cyclodextrin derivatives containing a 3, 4 or 5 membered ether-linked bridge between the 6A and 6D oxygen atoms, with and without a ketone, were prepared. The synthesis used perbenzylated alpha-cyclodextrin A,D-diol as a starting material upon which O-alkylation and further modi...... derivatives were also made. The 6A,6D-di-O-(propa-2-on-1,3-diyl)-6C,6F-di-O-methyl and di-O-pivaloyl derivatives were also prepared. The new compounds were analysed for catalysis of the oxidation of amines and alcohols....

  15. Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

    Science.gov (United States)

    Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

    2017-12-01

    Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

  16. 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.

  17. 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.

  18. Optimization of transesterification of rubber seed oil using heterogeneous catalyst calcium oxide

    Science.gov (United States)

    Inggrid, Maria; Kristanto, Aldi; Santoso, Herry

    2015-12-01

    Biodiesel is an alternative fuel manufactured with the help of alkali hydroxide catalyst through transesterification reaction of vegetable oil. This study aims to examine methods and the most suitable conditions for transesterification reaction producing biodiesel from crude rubber seed oil by varying process parameters such as the molar ratio of alcohol, CaO amount as the alkaline catalyst, and reaction time. The rubber seed oil has a high level of free fatty acid content, which means the use of homogenous alkaline catalyst gives some technological problems such as soap formation which leaded in difficulty in the separation and purification of the product. Calcium oxide (CaO) is one of the most favorable heterogeneous base catalysts because it's reusable, noncorrosive, and low cost. Pre-treatment was performed by acid esterification with H2SO4 as the catalyst to decrease the content of free fatty acid in the rubber seed oil, in this pretreatment process the 12% FFA of crude oil could be reduced to below 3% FFA. The product after esterification process was then transesterified by alkaline transesterification by varying process parameters to convert triglyceride into biodiesel. The study found that maximum curvature for biodiesel yield occurred at 9:1 molar ratio of alcohol, 5%w catalyst loading, and 3 hours reaction time. Design expert software is used to determine the optimum point from experimental data. The result showed that the optimum yield of methyl ester from transesterification was 73.5 % by mass with 0.69 degree of desirability. The yielded methyl ester was tested for its density, viscosity, acid number, and solubility to meet SNI requirement standards.

  19. Calcium Oxide Derived from Waste Shells of Mussel, Cockle, and Scallop as the Heterogeneous Catalyst for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Achanai Buasri

    2013-01-01

    Full Text Available The waste shell was utilized as a bioresource of calcium oxide (CaO in catalyzing a transesterification to produce biodiesel (methyl ester. The economic and environmen-friendly catalysts were prepared by a calcination method at 700–1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD, X-ray fluorescence (XRF, scanning electron microscopy (SEM, and the Brunauer-Emmett-Teller (BET method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol.

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

    Directory of Open Access Journals (Sweden)

    Wu Chao

    2016-01-01

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