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Sample records for phase iron catalysts

  1. Nitrogen controlled iron catalyst phase during carbon nanotube growth

    Energy Technology Data Exchange (ETDEWEB)

    Bayer, Bernhard C., E-mail: bernhard.bayer@univie.ac.at [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Faculty of Physics, University of Vienna, A-1090 Vienna (Austria); Baehtz, Carsten [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Kidambi, Piran R.; Weatherup, Robert S.; Caneva, Sabina; Cabrero-Vilatela, Andrea; Hofmann, Stephan [Department of Engineering, University of Cambridge, Cambridge CB3 0FA (United Kingdom); Mangler, Clemens; Kotakoski, Jani; Meyer, Jannik C. [Faculty of Physics, University of Vienna, A-1090 Vienna (Austria); Goddard, Caroline J. L. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

    2014-10-06

    Close control over the active catalyst phase and hence carbon nanotube structure remains challenging in catalytic chemical vapor deposition since multiple competing active catalyst phases typically co-exist under realistic synthesis conditions. Here, using in-situ X-ray diffractometry, we show that the phase of supported iron catalyst particles can be reliably controlled via the addition of NH{sub 3} during nanotube synthesis. Unlike polydisperse catalyst phase mixtures during H{sub 2} diluted nanotube growth, nitrogen addition controllably leads to phase-pure γ-Fe during pre-treatment and to phase-pure Fe{sub 3}C during growth. We rationalize these findings in the context of ternary Fe-C-N phase diagram calculations and, thus, highlight the use of pre-treatment- and add-gases as a key parameter towards controlled carbon nanotube growth.

  2. Fe phase complexes and their thermal stability in iron phosphate catalysts supported on silica

    Energy Technology Data Exchange (ETDEWEB)

    Dasireddy, Venkata D. B. C., E-mail: dasireddy@gmail.com; Bharuth-Ram, K.; Harilal, A.; Singh, S.; Friedrich, H. B. [University of KwaZulu-Natal, School of Chemistry and Physics (South Africa)

    2015-04-15

    Comparative XRD and Mössbauer spectroscopy studies have been conducted on the effect of temperature on the phase transformations of an iron phosphate catalyst synthesized using the ammonia gel method (CAT1) and a commercial grade FePO {sub 4} catalyst supported on silica using wet impregnation method (CAT2). The XRD patterns of both catalysts showed the presence of iron phosphate and the tridymite phase of aluminum phosphate. Mössbauer spectra of the catalysts show that the phases present in CAT1 are thermally stable up to 500 {sup ∘}C, but CAT2 shows significant changes with the tridymite phase of iron phosphate increasing from 6 % to 29 % of the spectral area at a temperature of 500 {sup ∘}C.

  3. Disproportionation phenema of wistite phase in the model iron catalysts for ammonia synthesis studied by Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Pattek-Janczyk, A.; Miczko, B.

    1990-01-01

    A model iron catalysts for ammonia synthesis containing a large amount of wustite (35 wt%) has been studied during the annealing in an inert atmosphere in the temperature range of 573-773 K. Changes in magnetite and wustite phases were followed by Muessbauer spectroscopy (MS). Before starting the thermal treatment, two kinds of wustite of different structures have been found by MS and X-ray diffraction. The behaviour of both kinds of wustite during the annealing was different. One of them, closer to the stoichiometric compound, disproportionated at once into magnetite and iron; its content decreased systematically without changes in the Muessbauer parameters. In the second wustite, only qualitatieve changes were observed at first (its nonstoichiometry decreases without changes in content and, next, this phase started to disproportionate too. (auhtor). 31 refs.; 6 figs.; 2 tabs

  4. TECHNOLOGIES OF DOPING OF CAST IRON THROUGH THE SLAG PHASE WITH USING OF THE SPENT NICKEL- AND COPPER-CONTAINING CATALYSTS

    Directory of Open Access Journals (Sweden)

    I. B. Provorova

    2015-01-01

    Full Text Available We have defined the regularities of the doping of cast iron through the slag phase of nickel and copper due to the waste catalysts using a carbonaceous reducing agent. We have justified the need to use the cast iron chips as a seed in the composition of the slag mixture. We have defined the dependence of the degree of extraction of nickel or copper from spent catalyst on the amount of the catalyst, on the basicity of the slag mixture, on the temperature and time of melting.

  5. 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

  6. Ligand iron catalysts for selective hydrogenation

    Science.gov (United States)

    Casey, Charles P.; Guan, Hairong

    2010-11-16

    Disclosed are iron ligand catalysts for selective hydrogenation of aldehydes, ketones and imines. A catalyst such as dicarbonyl iron hydride hydroxycyclopentadiene) complex uses the OH on the five member ring and hydrogen linked to the iron to facilitate hydrogenation reactions, particularly in the presence of hydrogen gas.

  7. TECHNOLOGY DEVELOPMENT FOR IRON FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Davis, B.H.

    1998-07-22

    The goal of the proposed work described in this Final Report was the development of iron-based Fischer-Tropsch catalysts that combined high activity, selectivity and life with physical robustness for slurry phase reactors that will produce either low-alpha or high-alpha products. The work described here has optimized the catalyst composition and pretreatment operation for a low-alpha catalyst. In parallel, work has been conducted to design a high-alpha iron catalyst that is suitable for slurry phase synthesis. Studies have been conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors have been studied at the laboratory scale. Catalyst performance has been determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  8. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Burtron H. Davis

    1999-01-01

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe(sub 3)O(sub 4). Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to(epsilon)(prime)-Fe(sub 2.2)C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to(chi)-Fe(sub 5)C(sub 2) and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe(sub 3)O(sub 4); however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94%(chi)-Fe(sub 5)C(sub 2), deactivated rapidly as the carbide was oxidized to Fe(sub 3)O(sub 4). No difference in activity, stability or deactivation rate was found for(chi)-Fe(sub 5)C(sub 2) and(epsilon)(prime)-Fe(sub 2.2)C

  9. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Burtron H. Davis

    1999-04-30

    The impact of activation procedure on the phase composition of precipitated iron Fischer-Tropsch (FT) catalysts has been studied. Catalyst samples taken during activation and FT synthesis have been characterized by Moessbauer spectroscopy. Formation of iron carbide is necessary for high FT activity. Hydrogen activation of precipitated iron catalysts results in reduction to predominantly metallic iron and Fe{sub 3}O{sub 4}. Metallic iron is not stable under FT 3 4 conditions and is rapidly converted to {epsilon}{prime}-Fe{sub 2.2}C. Activation with carbon monoxide or syngas 2.2 with low hydrogen partial pressure reduces catalysts to {chi}-Fe{sub 5}C{sub 2} and a small amount of 5 2 superparamagnetic carbide. Exposure to FT conditions partially oxidizes iron carbide to Fe{sub 3}O{sub 4}; however, catalysts promoted with potassium or potassium and copper maintain a constant carbide content and activity after the initial oxidation. An unpromoted iron catalyst which was activated with carbon monoxide to produce 94% {chi}-Fe{sub 5}C{sub 2}, deactivated rapidly as the carbide was oxidized to Fe{sub 3}O{sub 4}. No difference in activity, stability or deactivation rate was found for {chi}-Fe{sub 5}C{sub 2} and {epsilon}{prime}-Fe{sub 2.2}C.

  10. Photoexcited iron porphyrin as biomimetic catalysts

    International Nuclear Information System (INIS)

    Bartocci, C.; Maldotti, A.; Varani, G.; Consiglio Nazionale delle Ricerche, Ferrara

    1996-01-01

    Photoexcited iron porphyrins can be of some interest in both fine and industrial chemistry in view of the preparation of new efficient biomimetic catalysts, working with high selectivity under mild temperature and pressure

  11. The obtaining of iron acetate from processed iron comprising catalyst of ammonia synthesis

    International Nuclear Information System (INIS)

    Mansurov, M.M.; Lugovenko, A.N.; Mirzoeva, M.M.

    1993-01-01

    Present article is devoted to obtaining of iron acetate from processed iron comprising catalyst of ammonia synthesis. The method of synthesis of iron acetate from processed iron comprising catalyst of ammonia synthesis was elaborated. The structure of complex was determined.

  12. Technology development for iron Fischer-Tropsch catalysts

    Energy Technology Data Exchange (ETDEWEB)

    O`Brien, R.J.; Raje, A.; Keogh, R.A. [and others

    1995-12-31

    The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alpha iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.

  13. Study of iron-zinc catalysts by Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Arriola, S.H.

    1990-01-01

    The Moessbauer parameters were determined on a series of catalyst mixtures of iron and zinc oxides with variable quantities of zinc. A change in the crystal structure of the iron oxide when introducing zinc into the samples was observed. The corundum structure of the α-Fe 2 O 3 phase was transformed into the spinel type of zinc ferrite when zinc oxide was present in any quantity. A strong electronic interaction between the zinc ferrite and the zinc oxide present in excess was evident. The catalysts were analyzed using x-ray fluorescence and x-ray diffraction methods. (author) 10 refs.; 4 figs.; 2 tabs

  14. Thermal effects in highly dispersed iron catalysts

    International Nuclear Information System (INIS)

    Alvarez, A.M.; Cagnoli, M.V.; Gallegos, N.G.; Marchetti, S.G.; Yeramian, A.A.; Mercader, R.C.

    1994-01-01

    The Moessbauer spectra of three Fe/SiO 2 catalysts with 5 wt% iron content show the presence of several Fe species and display different magnetic behaviours when the precursors are subjected to various thermal treatments. Based on the Moessbauer parameters and CO chemisorption measurements, the average crystal sizes of the catalysts are estimated and discussed in connection with the thermal pretreatment severity and magnetic properties of the samples. (orig.)

  15. An iron-57 Moessbauer spectroscopic study of titania-supported iron- and iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1992-01-01

    57 Fe Moessbauer spectroscopy shows that titania-supported iron is reduced by treatment in hydrogen at significantly lower temperatures than corresponding silica- and alumina-supported catalysts. The metallic iron formed under hydrogen at 600deg C is partially converted to carbide by treatment in carbon monoxide and hydrogen. In contrast to its alumina- and silica-supported counterparts, the remainder of the titania-supported iron is unchanged by this gaseous mixture. The 57 Fe Moessbauer spectra of EXAFS show that iron and iridium in the titania-supported iron-iridium catalysts are reduced in hydrogen at even lower temperatures and, after treatment at 600deg C, are predominantly present as the iron-iridium alloy. The treatment of these reduced catalysts in carbon monoxide and hydrogen is shown by Moessbauer spectroscopy and EXAFS to induce the segregation of iron from the iron-iridium alloy and its conversion to iron oxide. (orig.)

  16. DEVELOPMENT OF PRECIPITATED IRON FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Bukur, Dragomir B.; Lang, X.; Chokkaram, S.; Nowicki, L.; Wei, G.; Ding, Y.; Reddy, B.; Xiao, S.

    1999-01-01

    Despite the current worldwide oil glut, the US will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer-Tropsch (F-T) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Some of the F-T catalysts synthesized and tested at Texas A and M University under DOE Contract No. DE-AC22-89PC89868 were more active than any other known catalysts developed for maximizing production of high molecular weight hydrocarbons (waxes). The objectives of the present contract were to demonstrate repeatability of catalyst performance and reproducibility of preparation procedures of two of these catalysts on a laboratory scale. Improvements in the catalyst performance were attempted through the use of: (a) higher reaction pressure and gas space velocity to maximize the reactor productivity; (b) modifications in catalyst preparation steps; and (c) different pretreatment procedures. Repeatability of catalyst performance and reproducibility of catalyst synthesis procedure have been successfully demonstrated in stirred tank slurry reactor tests. Reactor space-time-yield was increased up to 48% by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while maintaining the gas contact time and synthesis gas conversion at a constant value. Use of calcination temperatures above 300 C, additional CaO promoter, and/or potassium silicate as the source of potassium promoter, instead of potassium bicarbonate, did not result in improved catalyst performance. By using different catalyst activation procedures they were able to increase substantially the catalyst activity, while maintaining low methane and gaseous hydrocarbon selectivities. Catalyst productivity in runs SA-0946 and SA-2186 was 0.71 and 0.86 gHC/g-Fe/h, respectively, and this represents 45-75% improvement in productivity relative to that achieved in Rheinpreussen's demonstration plant

  17. Carbon-supported iron and iron-molybdenum sulfide catalysts

    International Nuclear Information System (INIS)

    Ramselaar, W.L.T.M.

    1988-01-01

    The main objective was to describe the relations between the characteristics (composition and dispersion) of the actual sulfide phase and the catalytic activity. Attention was also paid to the influence of preparational aspects on these characteristics. The catalysts were characterized using in-situ Moessbauer spectroscopy down to 2.0 K. 254 refs.; 47 figs.; 22 tabs

  18. 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

  19. Synthetic production of fuels by the Fischer Tropsch reaction using iron catalysts

    International Nuclear Information System (INIS)

    Rodriguez Cepeda, Rodrigo; Pacheco Ochoa, Luis

    2004-01-01

    A series of iron catalysts were prepared on three different types of supports: alumina and two activated carbons from eucalyptus woods and tagua seeds. Potassium was used as promoter and palladium was deposited by the excess wetness impregnation method. The catalysts were characterized by N 2 adsorption at 77 K, XRD and TPR analysis and evaluated as Fischer-Tropsch catalysts. The carbon supported catalysts favour the production of liquid hydrocarbons and decrease the aqueous phase. Those supported with alumina form gases and aqueous phase as the main products. The α p parameters of the Schulz-Flory distribution show hydrocarbons between gasoline and diesel

  20. Moessbauer study on the formation process of Fe-K composition in iron-based catalyst for dehydrogenation of ethylbenzene

    International Nuclear Information System (INIS)

    Jiang Keyu; Zhao Zhenjie; Yang Xielong

    2001-01-01

    Fe-K spinel structure is the predecessor of active phase of potassium promoted iron-based catalyst for dehydrogenation of ethylbenzene. Moessbauer spectroscopy has been used to study the formation process of Fe-K spinel structure which depends on the catalyst composition and preparing condition. The results may prove useful for production of industrial catalyst

  1. DEVELOPMENT OF ATTRITION RESISTANT IRON-BASED FISCHER-TROPSCH CATALYSTS

    International Nuclear Information System (INIS)

    Adeyinka A. Adeyiga

    2001-01-01

    The Fischer-Tropsch (F-T) reaction provides a way of converting coal-derived synthesis gas (CO+H 2 ) to liquid fuels. Since the reaction is highly exothermic, one of the major problems in control of the reaction is heat removal. Recent work has shown that the use of slurry bubble column reactors (SBCRs) can largely solve this problem. The use of iron-based catalysts is attractive not only due to their low cost and ready availability, but also due to their high water-gas shift activity which makes it possible to use these catalysts with low H 2 /CO ratios. However, a serious problem with use of Fe catalysts in a SBCR is their tendency to undergo attrition. This can cause fouling/plugging of downstream filters and equipment, makes the separation of catalyst from the oil/wax product very difficult if not impossible, and results in a steady loss of catalyst from the reactor. Recently, fundamental understanding of physical attrition is being addressed by incorporating suitable binders into the catalyst recipe. This has resulted in the preparation of a spray dried Fe-based catalyst having aps of 70 mm with high attrition resistance. This Fe-based attrition resistant, active and selective catalyst gave 95% CO conversion through 125 hours of testing in a fixed-bed at 270 C, 1.48 MPa, H 2 /CO=0.67 and 2.0 NL/g-cat/h with C 5 + selectivity of >78% and methane selectivity of <5%. However, further development of the catalyst is needed to address the chemical attrition due to phase changes that any Fe-catalyst goes through potentially causing internal stresses within the particle and resulting in weakening, spalling or cracking. The objective of this research is to develop robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry bubble column reactor. Specifically we aim to develop to: (i) improve the performance and preparation procedure of the high activity, high attrition resistant, high alpha iron

  2. Iron-57 and iridium-193 Moessbauer spectroscopic studies of supported iron-iridium catalysts

    International Nuclear Information System (INIS)

    Berry, F.J.; Jobson, S.

    1988-01-01

    57 Fe and 193 Ir Moessbauer spectroscopy shows that silica- and alumina-supported iron-iridium catalysts formed by calcination in air contain mixtures of small particle iron(III) oxide and iridium(IV) oxide. The iridium dioxide in both supported catalysts is reduced in hydrogen to metallic iridium. The α-Fe 2 O 3 in the silica supported materials is predominantly reduced in hydrogen to an iron-iridium alloy whilst in the alumina-supported catalyst the iron is stabilised by treatment in hydrogen as iron(II). Treatment of a hydrogen-reduced silica-supported iron catalyst in hydrogen and carbon monoxide is accompanied by the formation of iron carbides. Carbide formation is not observed when the iron-iridium catalysts are treated in similar atmospheres. The results from the bimetallic catalysts are discussed in terms of the hydrogenation of associatively adsorbed carbon monoxide and the selectivity of supported iron-iridium catalysts to methanol formation. (orig.)

  3. 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

  4. Iron Contamination Mechanism and Reaction Performance Research on FCC Catalyst

    Directory of Open Access Journals (Sweden)

    Zhaoyong Liu

    2015-01-01

    Full Text Available FCC (Fluid Catalytic Cracking catalyst iron poisoning would not only influence units’ product slate; when the poisoning is serious, it could also jeopardize FCC catalysts’ fluidization in reaction-regeneration system and further cause bad influences on units’ stable operation. Under catalytic cracking reaction conditions, large amount of iron nanonodules is formed on the seriously iron contaminated catalyst due to exothermic reaction. These nodules intensify the attrition between catalyst particles and generate plenty of fines which severely influence units’ smooth running. A dense layer could be formed on the catalysts’ surface after iron contamination and the dense layer stops reactants to diffuse to inner structures of catalyst. This causes extremely negative effects on catalyst’s heavy oil conversion ability and could greatly cut down gasoline yield while increasing yields of dry gas, coke, and slurry largely. Research shows that catalyst’s reaction performance would be severely deteriorated when iron content in E-cat (equilibrium catalyst exceeds 8000 μg/g.

  5. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, N.B.; Kohler, S.; Harrington, M. [Sandia National Lab., Albuquerque, NM (United States)] [and others

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  6. Moessbauer and EXAFS studies of amorphous iron produced by thermal decomposition of carbonyl iron in liquid phase

    International Nuclear Information System (INIS)

    Nomura, Kiyoshi; Tanaka, Junichi; Ujihira, Yusuke; Takahashi, Tamotu; Uchida, Yasuzo

    1990-01-01

    Decomposition of iron carbonyl Fe(CO) 5 and Fe 2 (CO) 9 in liquid phase gave amorphous and crystalline iron powders in the absence and presence of catalyst, respectively. The hyperfine fields were large in amorphous phases prepared from Fe(CO) 5 than from Fe 2 (CO) 9 . Crystalline iron, iron carbide and a trace amount of Fe 3 O 4 were detected in the decomposition products of the amorphous phase prepared from Fe(CO) 5 , and iron carbide was mainly included in the decomposition products of the amorphous phase prepared from Fe 2 (CO) 9 . (orig.)

  7. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    Energy Technology Data Exchange (ETDEWEB)

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2004-03-31

    In this reporting period, a fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of production since the reaction is highly exothermic. Consequently, heavy wax products must be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase FTS. The separation problem is further compounded by catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. Existing pilot-scale equipment was modified to include a filtration test apparatus. After undergoing an extensive plant shakedown period, filtration tests with cross-flow filter modules using simulant FTS wax slurry were conducted. The focus of these early tests was to find adequate mixtures of polyethylene wax to simulate FTS wax. Catalyst particle size analysis techniques were also developed. Initial analyses of the slurry and filter permeate particles will be used by the research team to design improved filter media and cleaning strategies.

  8. 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.

  9. Novel, high-activity hydroprocessing catalysts: Iron group phosphides

    Science.gov (United States)

    Wang, Xianqin

    A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe2P, CoP and NO, were also prepared on a silica (SiO2) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N2 BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370°C). The reactivity studies showed that the nickel phosphide (Ni2P/SiO2) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/gamma-Al 2O3 catalyst at the same conditions, Ni2P/silica had a substantially higher HDS activity (100% vs. 76%) and HDN activity (82% vs. 38%). Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni2P/SiO 2, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%. Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni2P, but some sulfur was found to be retained after reaction. A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni2P/SiO2 sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an alpha-H activation

  10. Characterization of working iron Fischer-Tropsch catalysts using quantitative diffraction methods

    Science.gov (United States)

    Mansker, Linda Denise

    This study presents the results of the ex-situ characterization of working iron Fischer-Tropsch synthesis (F-TS) catalysts, reacted hundreds of hours at elevated pressures, using a new quantitative x-ray diffraction analytical methodology. Compositions, iron phase structures, and phase particle morphologies were determined and correlated with the observed reaction kinetics. Conclusions were drawn about the character of each catalyst in its most and least active state. The identity of the active phase(s) in the Fe F-TS catalyst has been vigorously debated for more than 45 years. The highly-reduced catalyst, used to convert coal-derived syngas to hydrocarbon products, is thought to form a mixture of oxides, metal, and carbides upon pretreatment and reaction. Commonly, Soxhlet extraction is used to effect catalyst-product slurry separation; however, the extraction process could be producing irreversible changes in the catalyst, contributing to the conflicting results in the literature. X-ray diffraction doesn't require analyte-matrix separation before analysis, and can detect trace phases down to 300 ppm/2 nm; thus, working catalyst slurries could be characterized as-sampled. Data were quantitatively interpreted employing first principles methods, including the Rietveld polycrystalline structure method. Pretreated catalysts and pure phases were examined experimentally and modeled to explore specific behavior under x-rays. Then, the working catalyst slurries were quantitatively characterized. Empirical quantitation factors were calculated from experimental data or single crystal parameters, then validated using the Rietveld method results. In the most active form, after pretreatment in H 2 or in CO at Pambient, well-preserved working catalysts contained significant amounts of Fe7C3 with trace alpha-Fe, once reaction had commenced at elevated pressure. Amounts of Fe3O 4 were constant and small, with carbide dpavg 65 wt%, regardless of pretreatment gas and pressure, with

  11. Technology development for iron F-T catalysts. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Frame, R.R.; Gala, H.B.

    1994-08-01

    The objectives of this work were twofold. The first objective was to design and construct a pilot plant for preparing precipitated iron oxide F-T precursors and demonstrate that the rate of production from this plant is equivalent to 100 lbs/day of dried metal oxide. Secondly, these precipitates were to be used to prepare catalysts capable of achieving 88% CO + H{sub 2} conversion with {le} 5 mole percent selectivity to methane + ethane.

  12. Deactivation by carbon of iron catalysts for indirect liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Bartholomew, C.H.

    1990-10-11

    This report describes recent progress in a fundamental, three-year investigation of carbon formation and its effects on the activity and selectivity of promoted iron catalysts for Fischer-Tropsch (FT) synthesis, the objectives of which are: determine rates and mechanisms of carbon deactivation of unsupported Fe and Fe/K catalysts during CO hydrogenation over a range of CO concentrations, CO:H{sub 2} ratios, and temperatures; model the rates of deactivation of the same catalysts in fixed-bed reactors. During the thirteenth quarter design of software for a computer-automated reactor system to be used in the kinetic and deactivation studies was continued. Further progress was made toward the completion of the control language, control routines, and software for operating this system. Progress was also made on the testing of the system hardware and software. H{sub 2} chemisorption capacities and activity selectivity data were also measured for three iron catalysts promoted with 1% alumina. 47 refs., 8 figs., 1 tab.

  13. Fabrication of Fischer-Tropsch Catalysts by Deposition of Iron Nanocrystals on Carbon Nanotubes

    NARCIS (Netherlands)

    Casavola, Marianna; Hermannsdoerfer, Justus; de Jonge, Niels; Dugulan, A. Iulian; de Jong, Krijn P.

    2015-01-01

    The fabrication of supported catalysts consisting of colloidal iron oxide nanocrystals with tunable size, geometry, and loadinghomogeneously dispersed on carbon nanotube (CNT) supportsis described herein. The catalyst synthesis is performed in a two-step approach. First, colloidal iron and iron

  14. Manganese and Iron Catalysts in Alkyd Paints and Coatings

    Directory of Open Access Journals (Sweden)

    Ronald Hage

    2016-04-01

    Full Text Available Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model alkyd curing using manganese and iron catalysts.

  15. Thermal decomposition of phase-stabilised ammonium nitrate (PSAM), HTPB based propellants. The effect of iron(III)oxide burning-rate catalyst

    NARCIS (Netherlands)

    Carvalheira, P.; Gadiot, G.M.H.J.L.; Klerk, W.P.C. de

    1995-01-01

    Phase-stabilised ammonium nitrate (PSAN) and hydroxyl-terminated polybutadiene (HTPB) are the main ingredients of propellants used with success in some pyrotechnic igniter components of the VULCAIN liquid rocket engine for the ARIANE 5. Small amounts of selected additives play an important role 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. Development of improved iron Fischer-Tropsch catalysts. Final technical report: Project 6464

    Energy Technology Data Exchange (ETDEWEB)

    Bukur, D.B.; Ledakowicz, S.; Koranne, M. [Texas A and M Univ., College Station, TX (United States). Dept. of Chemical Engineering] [and others

    1994-02-28

    Despite the current worldwide oil glut, the United States will ultimately require large-scale production of liquid (transportation) fuels from coal. Slurry phase Fischer Tropsch (FT) technology, with its versatile product slate, may be expected to play a major role in production of transportation fuels via indirect coal liquefaction. Texas A&M University (TAMU) with sponsorship from the US Department of Energy, Center for Energy and Mineral Resources at TAMU, Texas Higher Education Coordinating Board, and Air Products and Chemicals, Inc., has been working on development of improved iron FT catalysts and characterization of hydrodynamic parameters in two- and three-phase bubble columns with FT derived waxes. Our previous studies have provided an improved understanding of the role of promoters (Cu and K), binders (silica) and pretreatment procedures on catalyst activity, selectivity and longevity (deactivation). The objective of the present contract was to develop improved catalysts with enhanced slurry phase activity and higher selectivity to liquid fuels and wax. This was accomplished through systematic studies of the effects of pretreatment procedures and variations in catalyst composition (promoters and binders). The major accomplishments and results in each of these two main areas of research are summarized here.

  18. Effect of Drying Temperature on Iron Fischer-Tropsch Catalysts Prepared by Solvent Deficient Precipitation

    Directory of Open Access Journals (Sweden)

    Michael K. Albretsen

    2017-01-01

    Full Text Available A novel solvent deficient precipitation (SDP method to produce nanoparticles was studied for its potential in Fischer-Tropsch synthesis (FTS catalysis. Using Fe(NO33·9H2O as the iron-containing precursor, this method produces ferrihydrite particles which are then dried, calcined, reduced, and carbidized to form the active catalytic phase for FTS. Six different drying profiles, including final drying temperatures ranging between 80 and 150°C, were used to investigate the effect of ammonium nitrate (AN, a major by-product of reaction between Fe(NO33·9H2O and NH4HCO3 in the SDP method. Since AN has two phase-transitions within this range of drying temperatures, three different AN phases can exist during the drying of the catalyst precursors. These AN phases, along with physical changes occurring during the phase transitions, may affect the pore structure and the agglomeration of ferrihydrite crystallites, suggesting possible reasons for the observed differences in catalytic performance. Catalysts dried at 130°C showed the highest FTS rate and the lowest methane selectivity. In general, better catalytic performance is related to the AN phase present during drying as follows: phase III > phase II > phase I. However, within each AN phase, lower drying temperatures led to better catalytic properties.

  19. Directed plant cell-wall accumulation of iron: embedding co-catalyst for efficient biomass conversion

    Science.gov (United States)

    Chien-Yuan Lin; Joseph E. Jakes; Bryon S. Donohoe; Peter N. Ciesielski; Haibing Yang; Sophie-Charlotte Gleber; Stefan Vogt; Shi-You Ding; Wendy A. Peer; Angus S. Murphy; Maureen C. McCann; Michael E. Himmel; Melvin P. Tucker; Hui Wei

    2016-01-01

    Background: Plant lignocellulosic biomass is an abundant, renewable feedstock for the production of biobased fuels and chemicals. Previously, we showed that iron can act as a co-catalyst to improve the deconstruction of lignocellulosic biomass. However, directly adding iron catalysts into biomass prior to pretreatment is diffusion limited,...

  20. 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.

  1. Preparation of Fischer-Tropsch catalysts from cobalt/iron hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Howard, B.H.; Boff, J.J.; Zarochak, M.F. [Pittsburgh Energy Technology Center, PA (United States)] [and others

    1995-12-31

    Compounds with the (hydrotalcites) have properties that make them attractive as precursors for Fischer-Tropsch catalysts. A series of single-phase hydrotalcites with cobalt/iron atom ratios ranging from 75/25 to 25/75 has been synthesized. Mixed cobalt/iron oxides have been prepared from these hydrotalcites by controlled thermal decomposition. Thermal decomposition at temperatures below 600 {degrees}C typically produced a single-phase mixed metal oxide with a spinel structure. The BET surface areas of the spinal samples have been found to be as high as about 150 m{sup 2}/g. Appropriate reducing pretreatments have been developed for several of these spinels and their activity, selectivity, and activity and selectivity maintenance have been examined at 13 MPa in a fixed-bed microreactor.

  2. Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

    Science.gov (United States)

    Sapienza, R.S.; Slegeir, W.A.

    1990-05-15

    This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

  3. Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol over Nitrogen-Doped Carbon-Supported Iron Catalysts.

    Science.gov (United States)

    Li, Jiang; Liu, Jun-Ling; Zhou, Hong-Jun; Fu, Yao

    2016-06-08

    Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen-iron species, the presence of crystallized Fe2 O3 phase, and the pore structure change were the main reasons for catalyst deactivation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Application of Moessbauer spectroscopy for the characterization of iron-containing catalysts

    International Nuclear Information System (INIS)

    Phillips, J.

    1998-01-01

    Work in our laboratory demonstrates the unique analytical power as well as the limits of Moessbauer Spectroscopy (MES) as a tool for characterizing the size and phase of supported iron containing catalyst particles, particularly carbon supported catalysts. The major challenge in employing MES to characterize catalytic particles is understanding the impact of the relaxation effects on the spectra. Proper methods yield particle size and phase information, whereas improper interpretation can lead to the misidentification of phases. This is illustrated by feeding ersatz 'relaxed' spectra data, generated mathematically with a program which accounts for all aspects of relaxation, to a standard fitting routine. The fitting routine misinterprets the data and provides false phase identification. Methods for recognizing relaxation phenomena and strategies for extracting correct information from relaxed spectra are reviewed. Also reviewed are the major findings of studies on carbon supported catalysts. For example, MES studies, in conjunction with other techniques, demonstrate that bulk and surface structures which are easily accessible for carbon supported bimetallics are generally not found on refractory oxides

  5. Effect of iron catalyst thickness on vertically aligned carbon nanotube forest straightness for CNT-MEMS

    International Nuclear Information System (INIS)

    Moulton, Kellen; Jensen, Brian D; Morrill, Nicholas B; Konneker, Adam M; Vanfleet, Richard R; Allred, David D; Davis, Robert C

    2012-01-01

    This paper examines the effect of iron catalyst thickness on the straightness of growth of carbon nanotubes (CNTs) for microelectromechanical systems fabricated using the CNT-templated-microfabrication (CNT-M) process. SEM images of samples grown using various iron catalyst thicknesses show that both straight sidewalls and good edge definition are achieved using an iron thickness between 7 and 8 nm. Below this thickness, individual CNTs are well aligned, but the sidewalls of CNT forests formed into posts and long walls are not always straight. Above this thickness, the CNT forest sidewalls are relatively straight, but edge definition is poor, with significantly increased sidewall roughness. The proximity of a device or feature to other regions of iron catalyst also affects CNT growth. By using an iron catalyst thickness appropriate for straight growth, and by adding borders of iron around features or devices, a designer can greatly improve straightness of growth for CNT-MEMS. (paper)

  6. 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

  7. The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

    International Nuclear Information System (INIS)

    Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

    2010-01-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  8. A Systematic Modelling Framework for Phase Transfer Catalyst Systems

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Sales-Cruz, Mauricio; Hyung Kim, Sun

    2016-01-01

    Phase-transfer catalyst systems contain two liquid phases, with a catalyst (PTC) that transfers between the phases, driving product formation in one phase and being regenerated in the other phase. Typically the reaction involves neutral species in an organic phase and regeneration involves ions i....... The application of the framework is made to two cases in order to highlight the performance and issues of activity coefficient models for predicting design and operation and the effects when different organic solvents are employed....

  9. Characterization of the impregnated iron based catalyst for direct coal liquefaction by EXAFS

    International Nuclear Information System (INIS)

    Yang Jianli; Zhun Jisheng; Liu Zhenyu; Zhong Bing

    2002-01-01

    Catalyst plays an important role in direct coal liquefaction (DCL). Iron catalysts are regarded as the most attractive catalysts for DCL. To maximize catalytic effect and minimize catalysts usage, ultra-fine size catalysts are preferred. The most effective catalysts are found to be those impregnated onto coal because of their high dispersion on coal surface and intimate contact with coal particles. Besides the physical size, chemical form of a catalyst or a catalyst precursor is also important in determination of DCL activity. The expended X-ray absorption fine structure spectroscopy technique were used in this study. It was shown that the catalysts tested are in nanomater range and have structure mainly in the form of γ-FeOOH and FeS, or possibly of Fe/O/S. The presence of γ-FeOOH can be attributed to the interaction between Fe and the oxygen containing groups of coal or oxygen from moisture

  10. Immobilization of molecular catalysts in supported ionic liquid phases.

    Science.gov (United States)

    Van Doorslaer, Charlie; Wahlen, Joos; Mertens, Pascal; Binnemans, Koen; De Vos, Dirk

    2010-09-28

    In a supported ionic liquid phase (SILP) catalyst system, an ionic liquid (IL) film is immobilized on a high-surface area porous solid and a homogeneous catalyst is dissolved in this supported IL layer, thereby combining the attractive features of homogeneous catalysts with the benefits of heterogeneous catalysts. In this review reliable strategies for the immobilization of molecular catalysts in SILPs are surveyed. In the first part, general aspects concerning the application of SILP catalysts are presented, focusing on the type of catalyst, support, ionic liquid and reaction conditions. Secondly, organic reactions in which SILP technology is applied to improve the performance of homogeneous transition-metal catalysts are presented: hydroformylation, metathesis reactions, carbonylation, hydrogenation, hydroamination, coupling reactions and asymmetric reactions.

  11. Mordenite - Type Zeolite SCR Catalysts with Iron or Copper

    DEFF Research Database (Denmark)

    2012-01-01

    Cu/mordenite catalysts were found to be highly active for the SCR of NO with NH3 and exhibited high resistance to alkali poisoning. Redox and acidic properties of Cu/mordenite were well preserved after poisoning with potassium unlike that of vanadium catalysts. Fe-mordenite catalysts also reveale...... to be essential requirements for the high alkali resistance. Mordenite-type zeolite based catalysts could therefore be attractive alternatives to conventional SCR catalysts for biomass fired power plant flue gas treatment....

  12. Co-Production of Electricity and Hydrogen Using a Novel Iron-based Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hilaly, Ahmad; Georgas, Adam; Leboreiro, Jose; Arora, Salil; Head, Megann; Trembly, Jason; Turk, Brian; Gupta, Raghubir

    2011-09-30

    The primary objective of this project was to develop a hydrogen production technology for gasification applications based on a circulating fluid-bed reactor and an attrition resistant iron catalyst. The work towards achieving this objective consisted of three key activities: Development of an iron-based catalyst suitable for a circulating fluid-bed reactor; Design, construction, and operation of a bench-scale circulating fluid-bed reactor system for hydrogen production; Techno-economic analysis of the steam-iron and the pressure swing adsorption hydrogen production processes. This report describes the work completed in each of these activities during this project. The catalyst development and testing program prepared and iron-based catalysts using different support and promoters to identify catalysts that had sufficient activity for cyclic reduction with syngas and steam oxidation and attrition resistance to enable use in a circulating fluid-bed reactor system. The best performing catalyst from this catalyst development program was produced by a commercial catalyst toll manufacturer to support the bench-scale testing activities. The reactor testing systems used during material development evaluated catalysts in a single fluid-bed reactor by cycling between reduction with syngas and oxidation with steam. The prototype SIP reactor system (PSRS) consisted of two circulating fluid-bed reactors with the iron catalyst being transferred between the two reactors. This design enabled demonstration of the technical feasibility of the combination of the circulating fluid-bed reactor system and the iron-based catalyst for commercial hydrogen production. The specific activities associated with this bench-scale circulating fluid-bed reactor systems that were completed in this project included design, construction, commissioning, and operation. The experimental portion of this project focused on technical demonstration of the performance of an iron-based catalyst and a

  13. Two Iron Complexes as Homogeneous and Heterogeneous Catalysts for the Chemical Fixation of Carbon Dioxide.

    Science.gov (United States)

    Karan, Chandan Kumar; Bhattacharjee, Manish

    2018-04-16

    Two new bimetallic iron-alkali metal complexes of amino acid (serine)-based reduced Schiff base ligand were synthesized and structurally characterized. Their efficacy as catalysts for the chemical fixation of carbon dioxide was explored. The heterogeneous version of the catalytic reaction was developed by the immobilization of these homogeneous bimetallic iron-alkali metal complexes in an anion-exchange resin. The resin-bound complexes can be used as recyclable catalysts up to six cycles.

  14. 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.

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

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  16. 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

  17. Iron on mixed zirconia-titania substrate F-T catalyst

    International Nuclear Information System (INIS)

    Dyer, P.N.; Nordquist, A.F.; Pierantozzi, R.

    1988-01-01

    This patent deals with a Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized

  18. 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.

  19. Moessbauer study of the evolution of a laterite iron mineral based catalyst: effect of the activation treatment

    International Nuclear Information System (INIS)

    Cubeiro, M.L.; Goldwasser, M.R.; Perez Zurita, M.J.; Franco, C.; Gonzalez-Jimenez, F.; Jaimes, E.

    1994-01-01

    The syngas reaction has been studied using a laterite iron mineral, promoted with K and Mn. In situ activation under syngas, as well as pre-treatment with H 2 followed by CO under mild and more severe conditions were tested. These activation procedures led to different iron phase compositions and to different catalytic selectivities. The C 2 -C 4 /CH 4 ratio was significantly lower for those catalysts which after reaction showed the presence of hexagonal carbide and magnetite compared to the solid, which showed the highest proportion of Haegg carbide. (orig.)

  20. 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

  1. 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...

  2. Effect of pre-heat treatment on a Fischer-Tropsch iron catalyst

    International Nuclear Information System (INIS)

    Rao, K.R.P.M.; Huggins, F.E.; Ganguly, B.; Mahajan, V.; Huffman, G.P.; Davis, B.; O'Brien, R.J.; Xu Liguang; Rao, V.U.S.

    1994-01-01

    Moessbauer spectroscopy was used to investigate the effect of heating the Fischer-Tropsch catalyst 100 Fe/5 Cu/4.2 K/24 SiO 2 in two different atmospheres while ramping the temperature of the catalyst from room temperature to 280 C in 5.5 h prior to pretreatment of the catalyst. Preheating in H 2 /CO = 0.7 gave rise to an iron (Fe 2+ ) silicate, while preheating in helium resulted in the formation of ε'-carbide Fe 2.2 C. Iron oxides and χ-carbide Fe 5 C 2 were also formed in both preheat treatments. (orig.)

  3. NOVEL SLURRY PHASE DIESEL CATALYSTS FOR COAL-DERIVED SYNGAS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Dragomir B. Bukur; Dr. Ketil Hanssen; Alec Klinghoffer; Dr. Lech Nowicki; Patricia O' Dowd; Dr. Hien Pham; Jian Xu

    2001-01-07

    This report describes research conducted to support the DOE program in novel slurry phase catalysts for converting coal-derived synthesis gas to diesel fuels. The primary objective of this research program is to develop attrition resistant catalysts that exhibit high activities for conversion of coal-derived syngas.

  4. Leaching behavior of lanthanum, nickel and iron from spent catalyst using inorganic acids

    Science.gov (United States)

    Astuti, W.; Prilitasari, N. M.; Iskandar, Y.; Bratakusuma, D.; Petrus, H. T. B. M.

    2018-01-01

    Highly technological applications of rare earth metals (REs) and scarcity of supply have become an incentive torecover the REs from various resources, which include high grade and low grade ores, as well as recycledwaste materials. Spent hydrocracking catalyst contain lanthanum and a variety of valuable metals such as nickel and iron. This study investigated the recovery of lanthanum, nickel and iron from spent hydrocracking catalyst by leaching using various inorganic acid (sulfuric acid, hydrochloric acid, and nitric acid). The effect of acid concentration, type of acid and leaching temperature was conducted to study the leaching behavior of each valuable metal from spent-catalyst. It has been shown that it is possible to recover more than 90% of lanthanum, however the leaching efficiency of nickel and iron in this process was very low. It can be concluded that the leaching process is selective for lanthanum recovery from hydrocracking spent-catalyst.

  5. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    Science.gov (United States)

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  6. X-ray emission spectroscopy study of iron silicate catalyst FeZSM-5

    International Nuclear Information System (INIS)

    Csencsits, R.; Lyman, C.E.; Gronsky, R.

    1988-03-01

    Iron silicate analogs of the zeolite ZMS-5 may be directly synthesized from iron silicate gels in a manner which differs slightly from the alumino-silicate ZSM-5. The resultant white, crystalline iron silicate is referred to as FeZSM-5 in the as-synthesized form. Thermal treatment removes the organic crystal-directing agent and moves some of the framework iron into non-framework sites producing the calcined form of the molecular sieve FeZSM-5. Homogeneity in the distribution of catalytic iron throughout the particles is desired in an optimal catalyst. Distribution of the iron throughout the framework in the as-synthesized forms would affect the final distribution of catalytic iron in the calcined and steamed forms; thus, the iron distribution throughout the as-synthesized and calcined forms of FeZSM-5 were studied using the high spatial resolution on the analytical electron microscope. 7 refs., 3 figs

  7. Iron sulphide containing hydrodesulfurization catalysts : Mössbauer study of the sulfidibility of alpha-iron(III) oxide

    NARCIS (Netherlands)

    Ramselaar, W.L.T.M.; Beer, de V.H.J.; Kraan, van der A.M.

    1988-01-01

    As a first step in the study of the sulphidation of carbon-supported iron oxide catalyst systems the sulphiding of a well-characterized, unsupported model compound, viz. a-Fe2O3(mean particle diameter ca. 50 nm) was investigated using in-situ Mössbauer spectroscopy and the temperature-programmed

  8. Iron alloy Fischer-tropsch catalysts--1. Oxidation-reduction studies of the Fe-Ni system

    Energy Technology Data Exchange (ETDEWEB)

    Unmuth, E.E.; Schwartz, L.H.; Butt, J.B.

    1980-01-01

    Catalysts containing 5% iron, nickel, or 4:1 iron-nickel on silica were hydrogen-reduced at 425/sup 0/C for 12 or 24 hr, reoxidized in air for 2 or 4 hr, reduced again in hydrogen for 12 hr, and studied at each treatment step by Moessbauer spectroscopy, X-ray diffraction, and temperature-programed desorption. The nickel was reduced directly to the metal, redispersed during the oxidation, and gave 20% smaller particles in the second reduction than in the first reduction. The ..cap alpha..-Fe/sub 2/O/sub 3/ reduced via an Fe/sub 3/O/sub 4/ intermediate and yielded approx. 70% metallic iron and the second reduction produced about the same particle size as the first reduction. The alloy catalyst reduced into a mixture of two phases, a face-centered cubic phase containing approx. 37.5% Ni, i.e., the bulk equilibrium value, and a body-centered cubic phase, and the particle sizes obtained in the first and second reductions were similar. The activation energies for the reduction were determined.

  9. 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

  10. Advanced Aqueous Phase Catalyst Development using Combinatorial Methods, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Combinatorial methods are proposed to develop advanced Aqueous Oxidation Catalysts (AOCs) with the capability to mineralize organic contaminants present in effluents...

  11. New iron pyridylamino-bis(phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates

    NARCIS (Netherlands)

    Taherimehr, Masoumeh; Sertã, João Paulo C.ardoso Costa; Kleij, Arjan W.; Whiteoak, Christopher J.; Pescarmona, Paolo P.

    2015-01-01

    The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high

  12. Chelating agent-assisted heat treatment of a carbon-supported iron oxide nanoparticle catalyst for PEMFC.

    Science.gov (United States)

    Liu, Shyh-Jiun; Huang, Chia-Hung; Huang, Chun-Kai; Hwang, Weng-Sing

    2009-08-28

    Iron complexes were supported on commercial carbon black and heat treated to create FeO(x)/C catalysts that showed a larger normalized current density and normalized power density than commercial Pt/C catalysts; the coordination number of the iron complexes used affected the formation of the active site for oxygen reduction in PEMFC.

  13. A Study of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry - Nanostructure - Performance

    Science.gov (United States)

    Workman, Michael J., Jr.

    Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed. There has been a significant amount of research effort directed toward the development of platinum-group metal free (PGM-free) catalysts, yet there is a lack of consensus on both the engineering parameters necessary to improve the technology and the fundamental science that would facilitate rational design. I have engaged in research on PGM-free catalysts based on inexpensive and abundant reagents, specifically: nicarbazin and iron. Catalysts made from these precursors have previously proven to be among the best PGM-free catalysts, but their continued advancement suffered from the same lack of understanding that besets all catalysts in this class. The work I have performed address both engineering concerns and fundamental underlying principles. I present results demonstrating correlations between physical structure, chemical speciation, and synthesis parameters, as well as addressing active site chemistry and likely locations. My research presented herein introduces new morphology analysis techniques and elucidates several key structure-to-property characteristics of catalysts derived from iron and nicarbazin. I discuss the development and application of a new length-scale specific surface analysis technique that allows for analysis of well-defined size ranges from a few nm to several microns. The existing technique of

  14. Iron-Mediated Homogeneous ICAR ATRP of Methyl Methacrylate under ppm Level Organometallic Catalyst Iron(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Jian Wu

    2016-01-01

    Full Text Available Atom Transfer Radical Polymerization (ATRP is an important polymerization process in polymer synthesis. However, a typical ATRP system has some drawbacks. For example, it needs a large amount of transition metal catalyst, and it is difficult or expensive to remove the metal catalyst residue in products. In order to reduce the amount of catalyst and considering good biocompatibility and low toxicity of the iron catalyst, in this work, we developed a homogeneous polymerization system of initiators for continuous activator regeneration ATRP (ICAR ATRP with just a ppm level of iron catalyst. Herein, we used oil-soluble iron (III acetylacetonate (Fe(acac3 as the organometallic catalyst, 1,1′-azobis (cyclohexanecarbonitrile (ACHN with longer half-life period as the thermal initiator, ethyl 2-bromophenylacetate (EBPA as the initiator, triphenylphosphine (PPh3 as the ligand, toluene as the solvent and methyl methacrylate (MMA as the model monomer. The factors related with the polymerization system, such as concentration of Fe(acac3 and ACHN and polymerization kinetics, were investigated in detail at 90 °C. It was found that a polymer with an acceptable molecular weight distribution (Mw/Mn = 1.43 at 45.9% of monomer conversion could be obtained even with 1 ppm of Fe(acac3, making it needless to remove the residual metal in the resultant polymers, which makes such an ICAR ATRP process much more industrially attractive. The “living” features of this polymerization system were further confirmed by chain-extension experiment.

  15. Iron ore catalysts for methane decomposition to make CO x free hydrogen and carbon nano material

    KAUST Repository

    Zhou, Lu; Enakonda, Linga Reddy; Li, Sheng; Gary, Daniel; Del-Gallo, Pascal; Mennemann, Christina; Basset, Jean-Marie

    2018-01-01

    In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were

  16. Catalytic decomposition of tar derived from wood waste pyrolysis using Indonesian low grade iron ore as catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Wicakso, Doni Rahmat [Chemical Engineering Department, Faculty of Engineering, Lambung Mangkurat University, Jalan A. Yani KM. 36 Banjarbaru, 70714, South Kalimantan (Indonesia); Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Sutijan; Rochmadi [Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Budiman, Arief, E-mail: abudiman@ugm.ac.id [Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Center for Energy Studies, Gadjah Mada University, Sekip K1A, Yogyakarta, 55281 (Indonesia)

    2016-06-03

    Low grade iron ore can be used as an alternative catalyst for bio-tar decomposition. Compared to other catalysts, such as Ni, Rd, Ru, Pd and Pt, iron ore is cheaper. The objective of this research was to investigate the effect of using low grade iron ore as catalyst for tar catalytic decomposition in fixed bed reactor. Tar used in this experiment was pyrolysis product of wood waste while the catalyst was Indonesian low grade iron ore. The variables studied were temperatures between 500 – 600 °C and catalyst weight between 0 – 40 gram. The first step, tar was evaporated at 450 °C to produce tar vapor. Then, tar vapor was flowed to fixed bed reactor filled low grade iron ore. Gas and tar vapor from reactor was cooled, then the liquid and uncondensable gas were analyzed by GC/MS. The catalyst, after experiment, was weighed to calculate total carbon deposited into catalyst pores. The results showed that the tar components that were heavy and light hydrocarbon were decomposed and cracked within the iron ore pores to from gases, light hydrocarbon (bio-oil) and carbon, thus decreasing content tar in bio-oil and increasing the total gas product. In conclusion, the more low grade iron ore used as catalyst, the tar content in the liquid decrease, the H{sup 2} productivity increased and calorimetric value of bio-oil increased.

  17. The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

    Energy Technology Data Exchange (ETDEWEB)

    Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

    2010-11-01

    This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

  18. FY 1990 Study Meeting of Catalyst (Iron system). Data; 1990 nendo shokubai kento kai (Tetsu kei) shiryo

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1991-03-01

    The FY 1990 Study Meeting of Iron-system Catalyst was held at NEDO on March 12, 1991, and the data were arranged. In the study meeting, papers titled as follows were made public: About the behavior of H{sub 2}S on iron-system catalyst by Muroran Institute of Technology; Results of the test on iron-system catalyst in the BCL project by Research Institute, Mitsubishi Kasei Corp.; Results of the test on iron-system catalyst by 2.4 t/d PDU by NKK; Results of the test on iron-system catalyst by 0.1 t/d BSU by Mitsui Engineering and Shipbuilding Co.; Results of the test on iron-system catalyst by 1 t/d PSU by Nippon Steel Corp.; Results of the research at Government Industrial Development Laboratory, Hokkaido, and the study; Results of the research at National Chemical Laboratory for Industry and the study; Results of the research at the University of Tokyo and the study; Details of the development of synthetic iron sulfide and the attainment up to now by Asahi Chemical Industry Co. Moreover, the plenary session was held on research items for the development of iron-system catalyst in future. (NEDO)

  19. TECHNOLOGY DEVELOPMENT FOR IRON AND COBALT FISCHER-TROPSCH CATALYSTS

    Energy Technology Data Exchange (ETDEWEB)

    Burtron H. Davis

    1999-01-30

    The effects of copper on Fischer-Tropsch activity, selectivity and water-gas shift activity were studied over a wide range of syngas conversion. Three catalyst compositions were prepared for this study: (a) 100Fe/4.6Si/1.4K, (b) 100Fe/4.6Si/0.10Cu/1.4K and (c) 100Fe/4.6Si/2.0Cu/1.4K. The results are reported in Task 2. The literature review for cobalt catalysts is approximately 90% complete. Due to the size of the document, it has been submitted as a separate report labeled Task 6.

  20. Halogen-Bonding-Assisted Iodosylbenzene Activation by a Homogenous Iron Catalyst

    DEFF Research Database (Denmark)

    de Sousa, David P.; Wegeberg, Christina; Vad, Mads Sørensen

    2016-01-01

    The iron(III) complex of hexadentate N,N,N′-tris(2-pyridylmethyl)ethylendiamine-N′-acetate (tpena−) is a more effective homogenous catalyst for selective sulfoxidation and epoxidation with insoluble iodosylbenzene, [PhIO]n, compared with soluble methyl-morpholine-N-oxide (NMO). We propose that two...

  1. The renaissance of iron-based Fischer–Tropsch synthesis: on the multifaceted catalyst deactivation behaviour

    NARCIS (Netherlands)

    de Smit, E.|info:eu-repo/dai/nl/304824232; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2008-01-01

    Iron-based Fischer–Tropsch catalysts, which are applied in the conversion of CO and H2 into longer hydrocarbon chains, are historically amongst the most intensively studied systems in heterogeneous catalysis. Despite this, fundamental understanding of the complex and dynamic chemistry of the

  2. Synthesis of carbon nanotubes by CVD method using iron and molybdenum-based catalysts supported on ceramic matrices

    International Nuclear Information System (INIS)

    Teixeira, Ana Paula de Carvalho

    2010-01-01

    Molybdenum is known for its synergistic effect in the synthesis of carbon nanotubes (CNs) by chemical vapor deposition (CVD method). When added to typical catalysts like iron, nickel, and cobalt, even in small quantities, it is increases the yield of these nanostructures. The presence of Mo also has an influence on the type and number of CN walls formed. Although this effect is widely documented in the literature, there is not yet a consensus about the mechanism of action of molybdenum in catalytic systems. The objective of the present work is to study the influence of molybdenum on the catalytic activity of iron nanoparticle-based catalysts supported on magnesium oxide (Fe/MgO system) in the synthesis of carbon nanotubes by the CVD method. The Mo concentration was systematically varied from null to molar ratio values four times greater than the quantity of Fe, and the obtained material (catalysts and carbon nanotubes) were broadly characterized by different techniques. In order to also study the influence of the preparation method on the final composition of the catalytic system phases, the catalytic systems (Fe/MgO e FeMo x /MgO) were synthesized by two different methods: co-precipitation and impregnation. The greatest CN yields were observed for the catalysts prepared by coprecipitation. The difference was attributed to better dispersion of the Fe and Mo phases in the catalyst ceramic matrix. In the precipitation stage, it was observed the formation of layered double hydroxides whose concentration increased with the Mo content up to the ratio of Mo/Fe equal to 0.2. This phase is related to a better distribution of Fe and Mo in this concentration range. Another important characteristic observed is that the ceramic matrix is not inert. It can react both with Fe and Mo and form the iron solid solution in the magnesium oxide and the phases magnesium-ferrite (MgFe 2 0 4 ) and magnesium molybdate (MgMo0 4 ). The MgFe 2 0 4 phase is observed in all catalytic systems

  3. The synthesis of nanostructured, phase pure catalysts by hydrodynamic cavitation

    Energy Technology Data Exchange (ETDEWEB)

    Moser, W.R.; Sunstrom, J.E.; Marshik-Geurts, B.J. [Worcester Polytechnic Institute, Worcester, MA (United States)

    1995-12-01

    A new process for the synthesis of advanced catalytic materials based on performing the synthesis under hydrodynamic cavitation conditions has been discovered. This continuous process for catalyst synthesis resulted in the formation of both supported and unsupported catalysts. The advantage of the process over classical methods of synthesis is that it permits the formation of a wide variety of nanostructured catalysts in exceptionally high phase purities. The synthesis of platinum and palladium catalysts supported on alumina and other supports resulted in high dispersions of the noble metals. The synthesis of alpha, beta- and gamma-bismuth molybdates resulted in catalysts having superior phase purities as compared to several other classical methods of synthesis. The beta-bismuth molybdate was synthesized directly onto Cabosil. These studies showed that the particle size of the active component could be varied from a few manometers to much larger grains. The process enabled the synthesis of other complex metal oxides like perovskites as pure phases. The process uses a commercially available Microfluidizer.

  4. 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.

  5. 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.

  6. 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.

  7. The role of the iron catalyst in the toxicity of multi-walled carbon nanotubes (MWCNTs).

    Science.gov (United States)

    Visalli, Giuseppa; Facciolà, Alessio; Iannazzo, Daniela; Piperno, Anna; Pistone, Alessandro; Di Pietro, Angela

    2017-09-01

    This study aimed to investigate the role of iron, used as a catalyst, in the biological response to pristine and functionalized multi-walled carbon nanotubes (p/fMWCNTs) with an iron content of 2.5-2.8%. Preliminarily, we assessed the pro-oxidant activity of MWCNTs-associated iron by an abiotic test. To evaluate iron bioavailability, we measured intracellular redox-active iron in A549 cells exposed to both MWCNT suspensions and to the cell medium preconditioned by MWCNTs, in order to assess the iron dissolution rate under physiological conditions. Moreover, in exposed cells, we detected ROS levels, 8-oxo-dG and mitochondrial function. The results clearly highlighted that MWCNTs- associated iron was not redox-active and that iron leakage did not occur under physiological conditions, including the oxidative burst of specialized cells. Despite this, in MWCNTs exposed cells, higher level of intracellular redox-active iron was measured in comparison to control and a significant time-dependent ROS increase was observed (P<0.01). Higher levels of 8-oxo-dG, a marker of oxidative DNA damage, and decreased mitochondrial function, confirmed the oxidative stress induced by MWCNTs. Based on the results we believe that oxidative damage could be attributable to the release of endogenous redox-active iron. This was due to the damage of acidic vacuolar compartment caused by endocytosis-mediated MWCNT internalization. Copyright © 2017 Elsevier GmbH. All rights reserved.

  8. 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.

  9. The influence of phase transfer catalyst structure on reaction selectivity

    International Nuclear Information System (INIS)

    Demlov, Eh.V.

    1995-01-01

    A concise review is given of systematic studies which are concerned with the tuning of regio, frequentio-, chemo-, and diastereoselectivity by the structure or type of phase transfer catalyst. Use of MEI as an alkylating agent is described. Refs. 36, figs. 11

  10. Effect of precipitating agent on the catalytic behaviour of precipitated iron catalysts

    International Nuclear Information System (INIS)

    Motjope, T.R.; Dlamini, H.T.; Pollak, H.; Coville, N.J.

    1999-01-01

    Iron precipitated catalysts have been prepared using different precipitating agents (NH 4 OH, K 2 CO 3 ) at different pH values. In situ Moessbauer (MES) study of the reduced catalyst prepared using NH 4 OH revealed the presence of superparamagnetic Fe 2+ , Fe 3+ and magnetically split α-Fe only, whereas the catalyst prepared with K 2 CO 3 also showed an extra magnetic sextuplet of Fe 3 O 4 . For both catalyst systems, in situ MES revealed that during Fischer-Tropsch synthesis α-Fe was converted into ε'-Fe 2,2 C and finally into χ-Fe 2,5 C when the synthesis time was increased. The rate of formation of hydrocarbons was observed to increase with the increase in the degree of carburisation with the NH 4 OH catalyst showing a higher rate of reaction. The K 2 CO 3 catalyst exhibited higher olefin selectivity than the NH 4 OH catalyst under similar pH conditions

  11. 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.

  12. Iron doped fibrous-structured silica nanospheres as efficient catalyst for catalytic ozonation of sulfamethazine.

    Science.gov (United States)

    Bai, Zhiyong; Wang, Jianlong; Yang, Qi

    2018-04-01

    Sulfonamide antibiotics are ubiquitous pollutants in aquatic environments due to their large production and extensive application. In this paper, the iron doped fibrous-structured silica (KCC-1) nanospheres (Fe-KCC-1) was prepared, characterized, and applied as a catalyst for catalytic ozonation of sulfamethazine (SMT). The effects of ozone dosage, catalyst dosage, and initial concentration of SMT were examined. The experimental results showed that Fe-KCC-1 had large surface area (464.56 m2 g -1 ) and iron particles were well dispersed on the catalyst. The catalyst had high catalytic performance especially for the mineralization of SMT, with mineralization ratio of about 40% in a wide pH range. With addition of Fe-KCC-1, the ozone utilization increased nearly two times than single ozonation. The enhancement of SMT degradation was mainly due to the surface reaction, and the increased mineralization of SMT was due to radical mechanism. Fe-KCC-1 was an efficient catalyst for SMT degradation in catalytic ozonation system.

  13. Restrictive liquid-phase diffusion and reaction in bidispersed catalysts

    International Nuclear Information System (INIS)

    Lee, S.Y.; Seader, J.D.; Tsai, C.H.; Massoth, F.E.

    1991-01-01

    In this paper, the effect of bidispersed pore-size distribution on liquid-phase diffusion and reaction in NiMo/Al 2 O 3 catalysts is investigated by applying two bidispersed-pore-structure models, the random-pore model and a globular-structure model, to extensive experimental data, which were obtained from sorptive diffusion measurements at ambient conditions and catalytic reaction rate measurements on nitrogen-containing compounds. Transport of the molecules in the catalysts was found to be controlled by micropore diffusion, in accordance with the random-pore model, rather than macropore diffusion as predicted by the globular-structure model. A qualitative criterion for micropore-diffusion control is proposed: relatively small macroporosity and high catalyst pellet density. Since most hydrotreating catalysts have high density, diffusion in these types of catalysts may be controlled by micropore diffusion. Accordingly, it is believed in this case that increasing the size of micropores may be more effective to reduce intraparticle diffusion resistance than incorporating macropores alone

  14. Amphiphilic phase-transforming catalysts for transesterification of triglycerides

    Science.gov (United States)

    Nawaratna, Gayan Ivantha

    Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

  15. Growth of carbon nanoflowers on glass slides using sparked iron as a catalyst

    International Nuclear Information System (INIS)

    Thongtem, Somchai; Singjai, Pisith; Thongtem, Titipun; Preyachoti, Suksawat

    2006-01-01

    Carbon nanotubes (CNTs) were grown on glass slides using iron as a catalyst. By using 6 kV voltage, iron wire with 0.5 mm in diameter was sparked for 1, 2, 10 and 100 times to form iron dots/islands on the slides. CNTs were subsequently grown in a gas mixture of 10 ml/s Ar and 0.1 ml/s C 2 H 2 at a temperature range of 700-900 K for 300 s (5 min). In scanning and transmission electron microscopies, the CNTs grown on iron dots appear like flowers composed of carbon with hexagonal structure. In addition, the effects of oxide and gold sputtering on the growth of CNTs were studied. Both have no major influence on the growth

  16. Moessbauer spectroscopy and nuclear inelastic scattering studies on polynuclear oxo-bridged iron catalyst-first results

    International Nuclear Information System (INIS)

    Rajagopalan, S.; Asthalter, T.; Rabe, V.; Buerck, U. van; Wagner, F. E.; Laschat, S.

    2008-01-01

    Polynuclear iron catalysts are interesting materials because of their novel properties. In the future they may help to replace high cost and hazardous heavy metal catalysts by efficient, non toxic and economic iron compounds. In this work, we present some preliminary results on a novel polynuclear oxo-bridged iron catalyst. The chemical environment of the metal species (Fe) was studied under Gif-type conditions (Fe catalyst/Zn/O 2 in pyridine/acetic acid) with cyclohexene as substrate. Such Gif-type catalysts are able to catalyse the selective oxidation of alkanes and alkenes. The characterization was done by Moessbauer spectroscopy and nuclear inelastic scattering. In order to identify the intermediate species during the reaction (selective oxidation using molecular O 2 ), a freeze-quench technique was used. This also helps to understand the kinetics of the chemical reaction.

  17. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama

    2018-01-18

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  18. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Sklyaruk, Jan; Jang, Yoon Kyung; Zubar, Viktoriia; Rueping, Magnus

    2018-01-01

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  19. 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

  20. Ultrasound assisted synthesis of iron doped TiO2 catalyst.

    Science.gov (United States)

    Ambati, Rohini; Gogate, Parag R

    2018-01-01

    The present work deals with synthesis of Fe (III) doped TiO 2 catalyst using the ultrasound assisted approach and conventional sol-gel approach with an objective of establishing the process intensification benefits. Effect of operating parameters such as Fe doping, type of solvent, solvent to precursor ratio and initial temperature has been investigated to get the best catalyst with minimum particle size. Comparison of the catalysts obtained using the conventional and ultrasound assisted approach under the optimized conditions has been performed using the characterization techniques like DLS, XRD, BET, SEM, EDS, TEM, FTIR and UV-Vis band gap analysis. It was established that catalyst synthesized by ultrasound assisted approach under optimized conditions of 0.4mol% doping, irradiation time of 60min, propan-2-ol as the solvent with the solvent to precursor ratio as 10 and initial temperature of 30°C was the best one with minimum particle size as 99nm and surface area as 49.41m 2 /g. SEM analysis, XRD analysis as well as the TEM analysis also confirmed the superiority of the catalyst obtained using ultrasound assisted approach as compared to the conventional approach. EDS analysis also confirmed the presence of 4.05mol% of Fe element in the sample of 0.4mol% iron doped TiO 2 . UV-Vis band gap results showed the reduction in band gap from 3.2eV to 2.9eV. Photocatalytic experiments performed to check the activity also confirmed that ultrasonically synthesized Fe doped TiO 2 catalyst resulted in a higher degradation of Acid Blue 80 as 38% while the conventionally synthesized catalyst resulted in a degradation of 31.1%. Overall, the work has clearly established importance of ultrasound in giving better catalyst characteristics as well as activity for degradation of the Acid Blue 80 dye. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. New way for iron introduction in LDH matrix used as catalysts for Friedel–Crafts reactions

    Directory of Open Access Journals (Sweden)

    S. Kerchiche

    2017-02-01

    Full Text Available The alkylation of toluene, reaction employing benzyl chloride as the alkylating agent over basic hydrotalcite materials: Fe–Mg–Al-LDH prepared by different synthesis methods, including the method of co-precipitation, impregnation and a new method called the method of intercalation by anion exchange in the lamellar space of the host structure LDH. Our prepared solids were characterized by chemical analysis, XRD analysis, BET method and thermogravimetric analysis (TGA and tested in the alkylation of toluene by benzyl chloride reaction. Fe–Mg–Al-LDH clay without or with calcination (at 773 K has been investigated. The catalyst derived from the hydrotalcite by its calcination at 773 K shows high catalytic activity for the alkylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the oxides of iron on the catalyst surface.

  2. 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

  3. Iron ore catalysts for methane decomposition to make CO x free hydrogen and carbon nano material

    KAUST Repository

    Zhou, Lu

    2018-03-27

    In this work, for the first time, iron ores with 91.7%–96.2% FeO, 1.3%–2.3% AlO, 1.2%–4.5% SiO, 1.3%–3.9% NaO, were studied directly as bulk catalysts for methane decomposition. By hydrogen pre-reduction at 850 °C, FeO species on iron ores were gradually reduced into FeO, FeO and then finally into Fe species. After reduction of 1.6 g of iron ore catalysts of 50 µm particle size with 100 mL/min pure H for 3.5 h at 850 °C, CMD life testing was conducted at 850 °C and GHSV of 3.75 L/g h and the catalyst showed a stable methane conversion for 5 h. When methane decomposition proceeded on Fe sites, FeC species would be formed to deposit graphite around themselves to finally form carbon nano onions. This carbon nano onions material showed excellent application for wastewater purification. All samples were fully characterized with XRF, XRD, H-TPR, TEM and Raman.

  4. Water detritiation: better catalysts for liquid phase catalytic exchange

    International Nuclear Information System (INIS)

    Braet, J.

    2005-01-01

    Fusion reactors are our hope for a clean nuclear energy. But as they shall handle huge amounts of tritium, 1.5 10 19 Bq GWth -1 a -1 or about 50 000 times more tritium than light water fission reactors, they need detritiation. Most tritium losses can be trapped as or can easily be transformed into tritiated water. Water detritiation is preferably based on the multiplication of the large equilibrium isotope effect during the exchange reaction of tritium between hydrogen gas and liquid water in a counter current trickle bed reactor. Such LPCE (Liquid Phase Catalytic Exchange) requires an efficient hydrophobic catalyst. SCK-CEN invented and developed such a catalyst in the past. In combination with an appropriate packing, different batches of this catalyst performed very well during years of extensive testing, allowing to develop the ELEX process for water detritiation at inland reprocessing plants. The main objectives of this study were to reproduce and possibly improve the SCK-CEN catalyst for tritium exchange between hydrogen and liquid water; and to demonstrate the high overall exchange rate and thus high detritiation factors that can be realized with it in a small and simple LPCE column under typical but conservative operating conditions

  5. Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization

    International Nuclear Information System (INIS)

    Neri, G.; Visco, A.M.; Galvagno, S.; Donato, A.; Panzalorto, M.

    1999-01-01

    Gold on iron oxides catalysts have been characterized by temperature programmed reduction (TPR) and X-ray diffraction spectroscopy (XRD). The influence of preparation method, gold loading and pretreatment conditions on the reducibility of iron oxides have been investigated. On the impregnated Au/iron oxide catalysts as well as on the support alone the partial reduction of Fe(III) oxy(hydroxides) to Fe 3 O 4 starts in the 550 and 700 K temperature range. On the coprecipitated samples, the temperature of formation of Fe 3 O 4 is strongly dependent on the presence of gold. The reduction temperature is lowered as the gold loading is increased. The reduction of Fe 3 O 4 to FeO occurs at about 900 K and is not dependent on the presence of gold and the preparation method. It is suggested that the effect of gold on the reducibility of the iron oxides is related to an increase of the structural defects and/or of the surface hydroxyl groups. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  6. Iron-based materials as tar cracking catalyst in waste gasification

    Energy Technology Data Exchange (ETDEWEB)

    Nordgreen, Thomas

    2011-07-01

    The treatment of municipal solid waste (MSW) in Sweden has changed during the past decades due to national legislation and European Union directives. The former landfills have more or less been abandoned in favour of material recycling and waste incineration. On a yearly basis approximately 2.2 million tonnes waste are incinerated in Sweden with heat recovery and to some extent also with electricity generation, though at a low efficiency. It is desirable to alter this utilisation and instead employ MSW as fuel in a fluid bed gasification process. Then electrical energy may be produced at a much higher efficiency. However, MSW contain about 1 % chlorine in the form of ordinary table salt (NaCl) from food scraps. This implies that the tar cracking catalyst, dolomite, which is normally employed in gasification, will suffer from poisoning if applied under such conditions. Then the tar cracking capacity will be reduced or vanish completely with time. Consequently, an alternative catalyst, more resistant to chlorine, is needed. Preliminary research at KTH has indicated that iron in its metallic state may possess tar cracking ability. With this information at hand and participating in the project 'Energy from Waste' an experimental campaign was launched. Numerous experiments were conducted using iron as tar cracking catalyst. First iron sinter pellets from LKAB were employed. They were reduced in situ with a stream of hydrogen before they were applied. Later iron-based granules from Hoeganaes AB were tested. These materials were delivered in the metallic state. In all tests the KTH atmospheric fluidised bed gasifier with a secondary catalytic reactor housing the catalytic material was deployed. Mostly, the applied fuel was birch. The results show that metallic iron possesses an intrinsic ability, almost in the range of dolomite, to crack tars. Calculations indicate that iron may be more resistant to chlorine than dolomite. The exploration of metallic iron

  7. Nuclear prehistory influence on irradiated metallic iron phase composition

    International Nuclear Information System (INIS)

    Alekseev, I.E.

    2007-01-01

    With application of different Moessbauer spectroscopy applications the phase composition of metallic iron after irradiation by both neutrons and charged particles were studied. Irradiation conditions, method of targets examination and phase composition of samples after irradiation were presented in tabular form. It is shown, that phase composition of irradiated metal is defined by nuclear prehistory. So, in a number of cases abnormals (stabilization of high- and low-temperature structural phases of iron at room temperature after irradiation end) were revealed

  8. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department

    2017-09-26

    To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.

  9. Use characterisation of a diatomite catalyst impregnated with iron in the heterogeneous catalytic ozonization process

    International Nuclear Information System (INIS)

    Garcia Herrera, Walter

    2014-01-01

    Advanced oxidation processes have had a promising option in the treatment of wastewater, mainly in the presence of emerging and persistent pollutants. Among these processes have highlighted the catalytic ozonization, which has showed positive results in water treatment. Heterogeneous catalytic ozonization was characterized using diatomite impregnated with iron at the Universidad de Costa Rica. Contaminant degradation model was quantified (spectrophotometrically) for ozonization process and catalytic ozonization with the catalyst studied (1.000 g / L) at three different pH 4, 7 and 10. The effect of the catalyst concentration in the solution (0.250, 0.500, 1000, 1500 and 2.000 g/L) was determined under the conditions of pH with better performance of the catalyst. Runs in the presence of tert-butyl alcohol (TBA), known hydroxyl radical scavenger were performed to evaluate the effect on ozone indirect reactions. The degree of mineralization obtained was measured in the catalytic process.The variation of the COD of the solution was quantified under the best working conditions obtained. Finally, the performance of the catalyst in 4 cycles of reuse was studied by monitoring the leached iron of the catalyst, which has turned out to be 12%. Most degradation of contaminant model in ozonization process was obtained at pH 10, in accordance with the above theory (Buhler, Stachelin, & Hoigne, 1984). In contrast, at pH 4 the catalyst has presented the best efficiency, to the 3 minutes the noncatalytic process was curettaged 35% of dye, while the catalytic process by 60% in the same time. The degradation of the contaminant was improved even in the case of noncatalytic process at pH 10, which the 3 minutes was degradated to 44%. The presence of the catalyst at initial pH of 7 and 10, has showed without significant improvements in the process. The solution concentration of catalyst has presented the best efficiency of degradation has been 2,000 g/L, which has increased 70% to 3

  10. Highly Selective Continuous Gas-Phase Methoxycarbonylation of Ethylene with Supported Ionic Liquid Phase (SILP) Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; Garcia Suárez, Eduardo José; Fehrmann, Rasmus

    2017-01-01

    Supported ionic liquid phase (SILP) technology was applied for the first time to the Pd-catalyzed continuous, gas-phase methoxycarbonylation of ethylene to selectively produce methyl propanoate (MP) in high yields. The influence of catalyst and reaction parameters such as, for example, ionic liquid...

  11. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

    2018-06-26

    It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

  12. Selective phenol methylation to 2,6-dimethylphenol in a fluidized bed of iron-chromium mixed oxide catalyst with o-cresol circulation.

    Science.gov (United States)

    Zukowski, Witold; Berkowicz, Gabriela; Baron, Jerzy; Kandefer, Stanisław; Jamanek, Dariusz; Szarlik, Stefan; Wielgosz, Zbigniew; Zielecka, Maria

    2014-01-01

    2,6-dimethylphenol (2,6-DMP) is a product of phenol methylation, especially important for the plastics industry. The process of phenol methylation in the gas phase is strongly exothermic. In order to ensure good temperature equalization in the catalyst bed, the process was carried out using a catalyst in the form of a fluidized bed - in particular, the commercial iron-chromium catalyst TZC-3/1. Synthesis of 2,6-dimethylphenol from phenol and methanol in fluidized bed of iron-chromium catalyst was carried out and the fluidization of the catalyst was examined. Stable state of fluidized bed of iron-chromium catalyst was achieved. The measured velocities allowed to determine the minimum flow of reactants, ensuring introduction of the catalyst bed in the reactor into the state of fluidization. Due to a high content of o-cresol in products of 2,6-dimethylphenol synthesis, circulation in the technological node was proposed. A series of syntheses with variable amount of o-cresol in the feedstock allowed to determine the parameters of stationary states. A stable work of technological node with o-cresol circulation is possible in the temperature range of350-380°C, and o-cresolin/phenolin molar ratio of more than 0.48. Synthesis of 2,6-DMP over the iron-chromium catalyst is characterized by more than 90% degree of phenol conversion. Moreover, the O-alkylation did not occur (which was confirmed by GC-MS analysis). By applying o-cresol circulation in the 2,6-DMP process, selectivity of more than 85% degree of 2,6-DMP was achieved. The participation levels of by-products: 2,4-DMP and 2,4,6-TMP were low. In the optimal conditions based on the highest yield of 2,6-DMP achieved in the technological node applying o-cresol circulation, there are 2%mol. of 2,4-DMP and 6%mol. of 2,4,6-TMP in the final mixture, whereas 2,4,6-TMP can be useful as a chain stopper and polymer's molar mass regulator during the polymerization of 2,6-DMP.

  13. Visible-light-driven methane formation from CO2 with a molecular iron catalyst

    Science.gov (United States)

    Rao, Heng; Schmidt, Luciana C.; Bonin, Julien; Robert, Marc

    2017-08-01

    Converting CO2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO2 to CO known, can also catalyse the eight-electron reduction of CO2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO2 photoreduction reaction, but a two-pot procedure that first reduces CO2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO2 under mild conditions.

  14. Role of iron catalyst impregnated by solvent swelling method in pyrolytic removal of coal nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, J.; Kusakabe, K.; Morooka, S.; Nielsen, M.; Furimsky, E. [Kyushu University, Fukuoka (Japan). Dept. of Chemical Science and Technology

    1995-11-01

    Organometallic iron precursors, ferrocene and ferric acetate, were impregnated into Illinois No. 6 (IL), Wyoming (WY) and Yallourn (YL) coals by solvent swelling technique in THF, ethanol, and a THF/ethanol binary solvent. Then iron-impregnated coals were pyrolyzed in a flow of helium at atmospheric pressure in a fixed bed and a thermobalance. Conversion of coal nitrogen to N{sub 2} was 20, 38 and 30% respectively, for original IL, WY, and YL coals. Iron formed from both precursors lowered the onset temperature of N{sub 2} evolution by 20-100{degree}C. When ferrocene was impregnated in coals at a concentration of 1.7-1.8 wt% as Fe, nitrogen conversion was increased to 52, 71 and 68% for IL, WY and YL coals, respectively. Ferric acetate impregnated into IL coal from THF/ethanol solution increased the nitrogen conversion much more than that from ethanol solution. The expansion of microporous coal structure by the swelling was essential for better dispersion of the catalyst precursor. The evolution of HCN as well as NH{sub 3} was effectively suppressed above 600{degree}C by the presence of iron but not influenced significantly by combinations of catalyst precursors and solvents. The increase in N{sub 2} yield was compensated by the decrease in nitrogen emitted as HCN and NH{sub 3} and in tar and char. The increase in CO evolution from the iron-impregnated IL coal at 600-800{degree}C was explained by catalytic rearrangement of aromatic structure of char, accompanying the removal of nitrogen as N{sub 2}. In a range of 600-750{degree}C, the evolution of CO as well as N{sub 2} from the other coals increased remarkably with a significant decrease in CO{sub 2} gasification in char microproes. 32 refs., 9 figs., 3 tabs.

  15. The role of palladium in iron based Fischer-Tropsch catalysts prepared by flame spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Minnermann, M.; Zielasek, V.; Baeumer, M. [Bremen Univ. (DE). Inst. of Applied and Physical Chemistry (IAPC); Pokhrei, S.; Maedler, L. [Bremen Univ. (DE). Foundation Inst. of Materials Science (IWT); Thiel, K. [Fraunhofer Institute for Manufactoring Technology and Applied Materials Research, Bremen (Germany)

    2011-07-01

    Flame spray pyrolysis (FSP) is a novel technique for the fabrication of nanostructured catalysts with far-reaching options to control structure and composition even in cases where complex composites need to be prepared. In this study, we took advantage of this technique to synthesize highly dispersed pure and Pd-doped iron oxide nanoparticles and investigated them as Fischer-Tropsch (FT) catalysts. By systematically varying the Pd content over a large range from 0.1 wt % to 10 wt %, we were able to directly analyze the influence of the Pd content on activity and selectivity. In addition to catalytic measurements, the structure and composition of the particles were characterized before and after these measurements, using transmission electron microscopy, adsorption measurements, X-ray diffraction and EXAFS. The comparison revealed, on the one hand, that small Pd clusters (diameter: 1-2 nm) evolve from initially homogeneously distributed Pd and, on the other hand, that the iron oxide transforms into iron carbides depending on the Pd content. The presence of Pd influences the particle size in the pristine samples (8 - 11 nm), resulting in specific surface areas that increase as the Pd content increases. However, after activation and reaction the specific surface areas become similar due to partial agglomeration and sintering. In a fixed bed FT reaction test, enhanced FT activity was observed with increasing Pd content while the selectivity shifts to longer chain hydrocarbons, mainly paraffins. (orig.)

  16. Bio-dissolution of Ni, V and Mo from spent petroleum catalyst using iron oxidizing bacteria.

    Science.gov (United States)

    Pradhan, Debabrata; Kim, Dong J; Roychaudhury, Gautam; Lee, Seoung W

    2010-01-01

    Bioleaching studies of spent petroleum catalyst containing Ni, V and Mo were carried out using iron oxidizing bacteria. Various leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size were studied to evaluate their effects on the leaching efficiency as well as the kinetics of dissolution. The percentage of leaching of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH(4))Fe(3)(SO(4))(2)(OH)(6). Apart from this, the lower leaching efficiency of Mo was due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst. The diffusivities of the attacking species for Ni, V and Mo were also calculated.

  17. Moessbauer study of CO-precipitated Fischer-Tropsch iron catalysts

    International Nuclear Information System (INIS)

    Rao, K.R.P.M.; Huggins, F.E.; Mahajan, V.; Huffman, G.P.; Bukur, D.B.; Rao, V.U.S.

    1994-01-01

    Moessbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/x SiO 2 , where x = 0, 8, 16, 24, 25, 40, or 100, have shown that reduction of the oxide precursor in CO gives rise to χ-carbide Fe 5 C 2 whose amount decreases with an increase of SiO 2 content. The χ-carbide is converted into magnetite Fe 3 O 4 while catalyzing the FT synthesis reaction. A correlation between FT activity and the content of χ-carbide in the catalysts was found, which indicated that χ-carbide is active for FT synthesis reaction. (orig.)

  18. Graphitic Layer Encapsulated Iron Based Non‐precious Catalysts for the Oxygen Reduction Reaction

    DEFF Research Database (Denmark)

    Zhong, Lijie

    consisting of uniform metallic nanoparticles encapsulated in graphitic layers. The thesis work is conducted aiming at three major objectives: further optimization of the pyrolysis to achieve improved performance of catalysts, investigation of the complex Fe-containing components, and exploration...... of the nitrogen functionalities. Two anions in the electrolyte are used to probe the iron containing active sites towards the ORR, cyanide (CN-) in alkaline and thiocyanate (SCN-) in acidic medium, which seem supporting the above conclusions. These findings provide new insights to the encapsulation structure...

  19. ANALYSIS OF KINETICS OF CAST IRON ALLOYING THROUGH SLAG PHASE

    Directory of Open Access Journals (Sweden)

    O. S. Komarov

    2012-01-01

    Full Text Available The mechanism of cast iron alloying through slag phase due to use of nickel and copper oxides is considered and the analysis of kinetics regularity of alloying in case of absence of fuse in the form of milled cast-iron chips in slag and at their presence in it is carried out.

  20. High-BTU gas production from tar-bearing hot coke oven gas over iron catalyst

    Energy Technology Data Exchange (ETDEWEB)

    L.Y. Li; K. Morishita; T. Takarada [Gunma University, Gunma (Japan). Department of Biological and Chemical Engineering

    2005-07-01

    To utilize the tar-bearing hot coke oven gas (the by-product of coke making process) more effectively, a process was developed by converting the hot coke oven gas into a methane rich high-BTU gas over iron-bearing catalysts. The catalytic behaviour of Indonesian limonite ore was mainly discussed. For a reference, a conventional nickel catalyst (Ni/Al{sub 2}O{sub 3}) was employed. Laboratory scale tests were carried out in a two-stage fixed-bed reactor at ambient pressure. A bituminous coal sample was heated at first stage, the volatiles was carried by feed gas and decomposed at second stage. The limonite promoted hydropyrolysis of coal volatiles similar to Ni/Al{sub 2}O{sub 3} catalyst. High yields of total product gas and methane were obtained at 50 vol.% hydrogen atmosphere with a feed gas of 60 ml min{sup -1} hydrogen and 60 ml min{sup -1} nitrogen. After experiments, hydrocarbons heavier than ethane were not observed. Also that, carbon balance was more than 99.8% in coal char, product gases and carbon deposits. It was considered that coal volatiles converted into light gases and carbon almost completely in catalyst bed. Yields of product gas and methane depended upon catalytic temperature. At 923 K, the maximum yield of product gas was achieved at 74.3% for limonite catalyst on carbon balance with methane 83.2 vol.% of the carbonaceous gas products. Comparing with limonite, Fe/Al{sub 2}O{sub 3} and BOF dust samples showed low activities on coal volatiles catalytic decomposition. 21 refs., 5 figs., 3 tabs.

  1. Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil material to produce effective heterogeneous Fenton catalyst

    International Nuclear Information System (INIS)

    Manzo, Valentina; Pizarro, Carmen; Rubio, María Angélica; Cavalcante, Luis Carlos Duarte; Garg, Vijayendra Kumar; Fabris, José Domingos

    2011-01-01

    A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes φ   − 1 NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Mössbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H 2 O 2 decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 ± 0.4 and 23.3 ± 0.2 mass%, respectively). 298 K-Mössbauer patterns were similar for both samples, with a central (super)paramagnetic Fe 3 +  doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H 2 O 2 than that with five treatments.

  2. Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

    Science.gov (United States)

    Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

    2018-03-07

    The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

  3. Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

    Science.gov (United States)

    Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

    2018-03-26

    Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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

  5. Solid - solid and solid - liquid phase transitions of iron and iron alloys under laser shock compression

    Science.gov (United States)

    Harmand, M.; Krygier, A.; Appel, K.; Galtier, E.; Hartley, N.; Konopkova, Z.; Lee, H. J.; McBride, E. E.; Miyanishi, K.; Nagler, B.; Nemausat, R.; Vinci, T.; Zhu, D.; Ozaki, N.; Fiquet, G.

    2017-12-01

    An accurate knowledge of the properties of iron and iron alloys at high pressures and temperatures is crucial for understanding and modelling planetary interiors. While Earth-size and Super-Earth Exoplanets are being discovered in increasingly large numbers, access to detailed information on liquid properties, melting curves and even solid phases of iron and iron at the pressures and temperatures of their interiors is still strongly limited. In this context, XFEL sources coupled with high-energy lasers afford unique opportunities to measure microscopic structural properties at far extreme conditions. Also the achievable time resolution allows the shock history and phase transition mechanisms to be followed during laser compression, improving our understanding of the high pressure and high strain experiments. Here we present recent studies devoted to investigate the solid-solid and solid-liquid transition in laser-shocked iron and iron alloys (Fe-Si, Fe-C and Fe-O alloys) using X-ray diffraction and X-ray diffuse scattering. Experiment were performed at the MEC end-station of the LCLS facility at SLAC (USA). Detection of the diffuse scattering allowed the identification of the first liquid peak position along the Hugoniot, up to 4 Mbar. The time resolution shows ultrafast (between several tens and several hundreds of picoseconds) solid-solid and solid-liquid phase transitions. Future developments at XFEL facilities will enable detailed studies of the solid and liquid structures of iron and iron alloys as well as out-of-Hugoniot studies.

  6. Simulation of the catalyst layer in PEMFC based on a novel two-phase lattice model

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Jiejing; Yang Wei; Xu Li [School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072 (China); Wang Yuxin, E-mail: yxwang@tju.edu.cn [School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072 (China)

    2011-08-01

    Highlights: > We propose a novel two phase lattice model of catalyst layer in PEMFC. > The model features a catalyst phase and a mixed ionomer and pores phase. > Transport and electrochemical reaction in the lattice are simulated. > The model enables more accurate results than pore-solid two phase model. > Profiles of oxygen level and reaction rate across catalyst layer vary with cell current. - Abstract: A lattice model of catalyst layer in proton exchange membrane fuel cells (PEMFCs), consisting of randomly distributed catalyst phase (C phase) and mixed ionomer-pore phase (IP phase), was established by means of Monte Carlo method. Transport and electrochemical reactions in the model catalyst layer were calculated. The newly proposed C-IP model was compared with previously established pore-solid two phase model. The variation of oxygen level and reaction rate along the thickness of catalyst layer with cell current was discussed. The effect of ionomer distribution across catalyst layer was studied by comparing profiles of oxygen level, reaction rate and overpotential, as well as corresponding polarization curves.

  7. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

    Science.gov (United States)

    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

    2013-04-28

    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

  8. Unified Phase Diagram for Iron-Based Superconductors.

    Science.gov (United States)

    Gu, Yanhong; Liu, Zhaoyu; Xie, Tao; Zhang, Wenliang; Gong, Dongliang; Hu, Ding; Ma, Xiaoyan; Li, Chunhong; Zhao, Lingxiao; Lin, Lifang; Xu, Zhuang; Tan, Guotai; Chen, Genfu; Meng, Zi Yang; Yang, Yi-Feng; Luo, Huiqian; Li, Shiliang

    2017-10-13

    High-temperature superconductivity is closely adjacent to a long-range antiferromagnet, which is called a parent compound. In cuprates, all parent compounds are alike and carrier doping leads to superconductivity, so a unified phase diagram can be drawn. However, the properties of parent compounds for iron-based superconductors show significant diversity and both carrier and isovalent dopings can cause superconductivity, which casts doubt on the idea that there exists a unified phase diagram for them. Here we show that the ordered moments in a variety of iron pnictides are inversely proportional to the effective Curie constants of their nematic susceptibility. This unexpected scaling behavior suggests that the magnetic ground states of iron pnictides can be achieved by tuning the strength of nematic fluctuations. Therefore, a unified phase diagram can be established where superconductivity emerges from a hypothetical parent compound with a large ordered moment but weak nematic fluctuations, which suggests that iron-based superconductors are strongly correlated electron systems.

  9. Unified Phase Diagram for Iron-Based Superconductors

    Science.gov (United States)

    Gu, Yanhong; Liu, Zhaoyu; Xie, Tao; Zhang, Wenliang; Gong, Dongliang; Hu, Ding; Ma, Xiaoyan; Li, Chunhong; Zhao, Lingxiao; Lin, Lifang; Xu, Zhuang; Tan, Guotai; Chen, Genfu; Meng, Zi Yang; Yang, Yi-feng; Luo, Huiqian; Li, Shiliang

    2017-10-01

    High-temperature superconductivity is closely adjacent to a long-range antiferromagnet, which is called a parent compound. In cuprates, all parent compounds are alike and carrier doping leads to superconductivity, so a unified phase diagram can be drawn. However, the properties of parent compounds for iron-based superconductors show significant diversity and both carrier and isovalent dopings can cause superconductivity, which casts doubt on the idea that there exists a unified phase diagram for them. Here we show that the ordered moments in a variety of iron pnictides are inversely proportional to the effective Curie constants of their nematic susceptibility. This unexpected scaling behavior suggests that the magnetic ground states of iron pnictides can be achieved by tuning the strength of nematic fluctuations. Therefore, a unified phase diagram can be established where superconductivity emerges from a hypothetical parent compound with a large ordered moment but weak nematic fluctuations, which suggests that iron-based superconductors are strongly correlated electron systems.

  10. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  11. Use of solid-phase salt catalysts in furfural preparation

    Energy Technology Data Exchange (ETDEWEB)

    Morozov, E.F.; Shkut, V.M.; Kebich, M.S.; Kuznetsova, T.A.

    1981-01-01

    The manufacture of furfural (I) from tanning waste, birch sawdust, or corncobs at 220-230 degrees in the presence of 2.0-3.0% double superphosphate, ammophos, (NH/sub 4/)/sub 2/SO/sub 4/, NH/sub 4/NO/sub 3/, or NH/sub 4/Cl was evaluated. Most of I is formed within 40 minutes in the presence of NH4NO3 or NH4Cl, and within 55 minutes in the presence of double superphosphate. The highest yield of I was obtained in the presence of NH4NO3 and/or NH4Cl. The solid-phase catalyst caused a little degradation of lignocellulose.

  12. Propene Hydroformylation by Supported Aqueous-phase Rh-NORBOS Catalysts

    DEFF Research Database (Denmark)

    Riisager, Anders; Eriksen, Kim Michael; Hjortkjær, Jes

    2003-01-01

    The gas-phase hydroformylation reaction of propene using supported aqueous-phase (SAP) Rh-NORBOS modified catalysts in a continuous flow reactor has been examined. SAP catalysts supported on six different support materials were made by wet impregnation using solutions of the precursor complex Rh(...

  13. IMPROVED IRON CATALYSTS FOR SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Dragomir B. Bukur; Dr. Lech Nowicki; Victor Carreto-Vazquez; Dr. Wen-Ping Ma

    2001-11-28

    PureVision Technology, Inc. (PureVision) of Fort Lupton, Colorado is developing a process for the conversion of lignocellulosic biomass into fuel-grade ethanol and specialty chemicals in order to enhance national energy security, rural economies, and environmental quality. Lignocellulosic-containing plants are those types of biomass that include wood, agricultural residues, and paper wastes. Lignocellulose is composed of the biopolymers cellulose, hemicellulose, and lignin. Cellulose, a polymer of glucose, is the component in lignocellulose that has potential for the production of fuel-grade ethanol by direct fermentation of the glucose. However, enzymatic hydrolysis of lignocellulose and raw cellulose into glucose is hindered by the presence of lignin. The cellulase enzyme, which hydrolyzes cellulose to glucose, becomes irreversibly bound to lignin. This requires using the enzyme in reagent quantities rather than in catalytic concentration. The extensive use of this enzyme is expensive and adversely affects the economics of ethanol production. PureVision has approached this problem by developing a biomass fractionator to pretreat the lignocellulose to yield a highly pure cellulose fraction. The biomass fractionator is based on sequentially treating the biomass with hot water, hot alkaline solutions, and polishing the cellulose fraction with a wet alkaline oxidation step. In September 2001 PureVision and Western Research Institute (WRI) initiated a jointly sponsored research project with the U.S. Department of Energy (DOE) to evaluate their pretreatment technology, develop an understanding of the chemistry, and provide the data required to design and fabricate a one- to two-ton/day pilot-scale unit. The efforts during the first year of this program completed the design, fabrication, and shakedown of a bench-scale reactor system and evaluated the fractionation of corn stover. The results from the evaluation of corn stover have shown that water hydrolysis prior to alkaline hydrolysis may be beneficial in removing hemicellulose and lignin from the feedstock. In addition, alkaline hydrolysis has been shown to remove a significant portion of the hemicellulose and lignin. The resulting cellulose can be exposed to a finishing step with wet alkaline oxidation to remove the remaining lignin. The final product is a highly pure cellulose fraction containing less than 1% of the native lignin with an overall yield in excess of 85% of the native cellulose. This report summarizes the results from the first year's effort to move the technology to commercialization.

  14. Size and Promoter Effects on Stability of Carbon-Nanofiber-Supported Iron-Based Fischer-Tropsch Catalysts

    NARCIS (Netherlands)

    Xie, Jingxiu; Torres Galvis, Hirsa; Koeken, Ard C J; Kirilin, Alexey; Dugulan, A Iulian; Ruitenbeek, Matthijs; de Jong, Krijn P

    2016-01-01

    The Fischer-Tropsch Synthesis converts synthesis gas from alternative carbon resources, including natural gas, coal, and biomass, to hydrocarbons used as fuels or chemicals. In particular, iron-based catalysts at elevated temperatures favor the selective production of C2-C4 olefins, which are

  15. Non-sensitized selective photochemical reduction of CO2 to CO under visible light with an iron molecular catalyst.

    Science.gov (United States)

    Rao, Heng; Bonin, Julien; Robert, Marc

    2017-03-02

    A substituted tetraphenyl iron porphyrin, bearing positively charged trimethylammonio groups at the para position of each phenyl ring, demonstrates its ability as a homogeneous molecular catalyst to selectively reduce CO 2 to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.

  16. Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

    Directory of Open Access Journals (Sweden)

    Fatemeh Rajabi

    2016-07-01

    Full Text Available Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15 have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs.

  17. Field-emission property of self-purification SiC/SiOx coaxial nanowires synthesized via direct microwave irradiation using iron-containing catalyst

    Science.gov (United States)

    Zhou, Qing; Yu, Yongzhi; Huang, Shan; Meng, Jiang; Wang, Jigang

    2017-07-01

    SiC/SiOx coaxial nanowires were rapidly synthesized via direct microwave irradiation in low vacuum atmosphere. During the preparation process, only graphite, silicon, silicon dioxide powders were used as raw materials and iron-containing substance was employed as catalyst. Comprehensive characterizations were employed to investigate the microstructure of the products. The results showed that a great quantity of coaxial nanowires with uniform sizes and high aspect ratio had been successfully achieved. The coaxial nanowires consist of a silicon oxide (SiOx) shell and a β-phase silicon carbide (β-SiC) core that exhibited in special tube brush like. In additional, nearly all the products were achieved in the statement of pure SiC/SiOx coaxial nanowires without the existence of metallic catalyst, indicating that the self-removal of iron (Fe) catalyst should be occurred during the synthesis process. Photoluminescence (PL) spectral analysis result indicated that such novel SiC/SiOx coaxial nanowires exhibited significant blue-shift. Besides, the measurement results of field-emission (FE) demonstrated that the SiC/SiOx coaxial nanowires had ultralow turn-on field and threshold field with values of 0.2 and 2.1 V/μm, respectively. The hetero-junction structure formed between SiOx shell and SiC core, lots of emission sites, as well as clear tips of the nanowires were applied to explain the excellent FE properties.[Figure not available: see fulltext.

  18. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    This work focuses on (1) searching/summarizing published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) preparation and characterization of unsupported iron catalysts with/without potassium/platinum promoters; (3) measurement of H{sub 2} and CO adsorption/dissociation kinetics on iron catalysts using transient methods; (3) analysis of the transient rate data to calculate kinetic parameters of early elementary steps in FTS; (4) construction of a microkinetic model of FTS on iron, and (5) validation of the model from collection of steady-state rate data for FTS on iron catalysts. Three unsupported iron catalysts and three alumina-supported iron catalysts were prepared by non-aqueous-evaporative deposition (NED) or aqueous impregnation (AI) and characterized by chemisorption, BET, temperature-programmed reduction (TPR), extent-of-reduction, XRD, and TEM methods. These catalysts, covering a wide range of dispersions and metal loadings, are well-reduced and relatively thermally stable up to 500-600 C in H{sub 2} and thus ideal for kinetic and mechanistic studies. Kinetic parameters for CO adsorption, CO dissociation, and surface carbon hydrogenation on these catalysts were determined from temperature-programmed desorption (TPD) of CO and temperature programmed surface hydrogenation (TPSR), temperature-programmed hydrogenation (TPH), and isothermal, transient hydrogenation (ITH). A microkinetic model was constructed for the early steps in FTS on polycrystalline iron from the kinetic parameters of elementary steps determined experimentally in this work and from literature values. Steady-state rate data were collected in a Berty reactor and used for validation of the microkinetic model. These rate data were fitted to 'smart' Langmuir-Hinshelwood rate expressions derived from a sequence of elementary steps and using a combination of fitted steady-state parameters and parameters specified from the transient

  19. Fischer-Tropsch Synthesis over Iron Manganese Catalysts: Effect of Preparation and Operating Conditions on Catalyst Performance

    Directory of Open Access Journals (Sweden)

    Ali A. Mirzaei

    2009-01-01

    molar basis which is the most active catalyst for the conversion of synthesis gas to light olefins. The effects of different promoters and supports with loading of optimum support on the catalytic performance of catalysts are also studied. It was found that the catalyst containing 50%Fe/50%Mn/5 wt.%Al2O3 is an optimum-modified catalyst. The catalytic performance of optimal catalyst has been studied in operation conditions such as a range of reaction temperatures, H2/CO molar feed ratios and a range of total pressures. Characterization of both precursors and calcined catalysts is carried out by powder X-ray diffraction (XRD, scanning electron microscopy (SEM, BET specific surface area and thermal analysis methods such as TGA and DSC.

  20. Iron phthalocyanine supported on amidoximated PAN fiber as effective catalyst for controllable hydrogen peroxide activation in oxidizing organic dyes

    International Nuclear Information System (INIS)

    Han, Zhenbang; Han, Xu; Zhao, Xiaoming; Yu, Jiantao; Xu, Hang

    2016-01-01

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H 2 O 2 activation. The amidoxime groups greatly helped to anchor Iron(II) phthalocyanine molecules onto the fiber through coordination interaction, which has been confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and UV diffuse reflectance spectroscopy analyses. Electron spin resonance studies indicate that the catalytic process of physically anchored Iron(II) phthalocyanine performed via a hydroxyl radical pathway, while the catalyst bonded Iron(II) phthalocyanine through coordination effect could selectively catalyze the H 2 O 2 decomposition to generate high-valent iron-oxo species. This may result from the amidoxime groups functioning as the axial fifth ligands to favor the heterolytic cleavage of the peroxide O−O bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H 2 O 2 . In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity.

  1. Iron phthalocyanine supported on amidoximated PAN fiber as effective catalyst for controllable hydrogen peroxide activation in oxidizing organic dyes

    Energy Technology Data Exchange (ETDEWEB)

    Han, Zhenbang, E-mail: hzbang@aliyun.com [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Key Laboratory of Advanced Textile Composite Materials, Ministry of Education of China, Tianjin 300387 (China); Han, Xu [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Zhao, Xiaoming, E-mail: zhaoxiaoming@tjpu.edu.cn [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China); Key Laboratory of Advanced Textile Composite Materials, Ministry of Education of China, Tianjin 300387 (China); Yu, Jiantao; Xu, Hang [School of Textiles, Tianjin Polytechnic University, Tianjin 300387 (China)

    2016-12-15

    Iron(II) phthalocyanine was immobilized onto amidoximated polyacrylonitrile fiber to construct a bioinspired catalytic system for oxidizing organic dyes by H{sub 2}O{sub 2} activation. The amidoxime groups greatly helped to anchor Iron(II) phthalocyanine molecules onto the fiber through coordination interaction, which has been confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and UV diffuse reflectance spectroscopy analyses. Electron spin resonance studies indicate that the catalytic process of physically anchored Iron(II) phthalocyanine performed via a hydroxyl radical pathway, while the catalyst bonded Iron(II) phthalocyanine through coordination effect could selectively catalyze the H{sub 2}O{sub 2} decomposition to generate high-valent iron-oxo species. This may result from the amidoxime groups functioning as the axial fifth ligands to favor the heterolytic cleavage of the peroxide O−O bond. This feature also enables the catalyst to only degrade the dyes adjacent to the catalytic active centers and enhances the efficient utilization of H{sub 2}O{sub 2}. In addition, this catalyst could effectively catalyze the mineralization of organic dyes and can be easily recycled without any loss of activity.

  2. Reduction and Immobilization of Potassium Permanganate on Iron Oxide Catalyst by Fluidized-Bed Crystallization Technology

    Directory of Open Access Journals (Sweden)

    Guang-Xia Li

    2012-03-01

    Full Text Available A manganese immobilization technology in a fluidized-bed reactor (FBR was developed by using a waste iron oxide (i.e., BT-3 as catalyst which is a by-product from the fluidized-bed Fenton reaction (FBR-Fenton. It was found that BT-3 could easily reduce potassium permanganate (KMnO4 to MnO2. Furthermore, MnO2 could accumulate on the surface of BT-3 catalyst to form a new Fe-Mn oxide. Laboratory experiments were carried out to investigate the KMnO4-reduction mechanism, including the effect of KMnO4 concentration, BT-3 dosage, and operational solution pH. The results showed that the pH solution was a significant factor in the reduction of KMnO4. At the optimum level, pHf 6, KMnO4 was virtually reduced in 10 min. A pseudo-first order reaction was employed to describe the reduction rate of KMnO4.

  3. Impact of H2/CO ratios on phase and performance of Mn-modified Fe-based Fischer Tropsch synthesis catalyst

    International Nuclear Information System (INIS)

    Ding, Mingyue; Yang, Yong; Li, Yongwang; Wang, Tiejun; Ma, Longlong; Wu, Chuangzhi

    2013-01-01

    Highlights: ► Decreasing H 2 /CO ratio facilitated the conversion of Fe 3 O 4 to iron carbides on the surface layers. ► The formation of surface carbonaceous species was promoted in higher CO partial pressure. ► The formation of iron carbides on the surface of Fe 3 O 4 provided the FTS active sites. ► Decreasing H 2 /CO ratio promoted the product shifting towards heavy hydrocarbons. - Abstract: Impacts of H 2 /CO ratios on both the bulky and surface compositions of an iron–manganese based catalyst were investigated by XRD, MES, N 2 -physisorption, XPS and LRS. Fischer–Tropsch (F–T) synthesis performances were studied in a slurry-phase continuously stirred tank reactor. The characterization results showed that the fresh catalyst was comprised of the hematite, which was converted firstly to Fe 3 O 4 , and then carburized to iron carbides in both the bulk and surface regions under different H 2 /CO ratios atmosphere. Pretreatment in lower H 2 /CO ratio facilitated the formation of iron carbides on the surface of magnetite and surface carbonaceous species. During the F–T synthesis reaction, the catalyst reduced in lower H 2 /CO ratio presented higher catalytic activity, which is assigned probably to the formation of more iron carbides (especially for χ-Fe 5 C 2 ) on the surface of magnetite. The increase of CO partial pressure promoted the product distribution shifting towards heavy hydrocarbons

  4. Crystallographic phases and magnetic properties of iron nitride films

    Energy Technology Data Exchange (ETDEWEB)

    Li, Guo-Ke [Department of Physics, Hebei Advanced Thin Films Laboratory, Hebei Normal University, Shijiazhuang 050024 (China); Department of Mathematics and Physics, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Liu, Yan; Zhao, Rui-Bin [Department of Physics, Hebei Advanced Thin Films Laboratory, Hebei Normal University, Shijiazhuang 050024 (China); Shen, Jun-Jie [Department of Mathematics and Physics, Shijiazhuang Tiedao University, Shijiazhuang 050043 (China); Wang, Shang; Shan, Pu-Jia; Zhen, Cong-Mian [Department of Physics, Hebei Advanced Thin Films Laboratory, Hebei Normal University, Shijiazhuang 050024 (China); Hou, Deng-Lu, E-mail: houdenglu@mail.hebtu.edu.cn [Department of Physics, Hebei Advanced Thin Films Laboratory, Hebei Normal University, Shijiazhuang 050024 (China)

    2015-08-31

    Iron nitride films, including single phase films of α-FeN (expanded bcc Fe), γ′-Fe{sub 4}N, ε-Fe{sub 3−x}N (0 ≤ x ≤ 1), and γ″-FeN, were sputtered onto AlN buffered glass substrates. It was found possible to control the phases in the films merely by changing the nitrogen partial pressure during deposition. The magnetization decreased with increased nitrogen concentration and dropped to zero when the N:Fe ratio was above 0.5. The experimental results, along with spin polarized band calculations, have been used to discuss and analyze the magnetic properties of iron nitrides. It has been demonstrated that in addition to influencing the lattice constant of the various iron nitrides, the nearest N atoms have a significant influence on the exchange splitting of the Fe atoms. Due to the hybridization of Fe-3d and N-2p states, the magnetic moment of Fe atoms decreases with an increase in the number of nearest neighbor nitrogen atoms. - Highlights: • Single phase γ′-Fe{sub 4}N, ε-Fe{sub 3−x}N, and γ″-FeN films were obtained using dc sputtering. • The phases in iron nitride films can be controlled by the nitrogen partial pressure. • The nearest N neighbors have a significant influence on the exchange splitting of Fe.

  5. Crystallographic phases and magnetic properties of iron nitride films

    International Nuclear Information System (INIS)

    Li, Guo-Ke; Liu, Yan; Zhao, Rui-Bin; Shen, Jun-Jie; Wang, Shang; Shan, Pu-Jia; Zhen, Cong-Mian; Hou, Deng-Lu

    2015-01-01

    Iron nitride films, including single phase films of α-FeN (expanded bcc Fe), γ′-Fe 4 N, ε-Fe 3−x N (0 ≤ x ≤ 1), and γ″-FeN, were sputtered onto AlN buffered glass substrates. It was found possible to control the phases in the films merely by changing the nitrogen partial pressure during deposition. The magnetization decreased with increased nitrogen concentration and dropped to zero when the N:Fe ratio was above 0.5. The experimental results, along with spin polarized band calculations, have been used to discuss and analyze the magnetic properties of iron nitrides. It has been demonstrated that in addition to influencing the lattice constant of the various iron nitrides, the nearest N atoms have a significant influence on the exchange splitting of the Fe atoms. Due to the hybridization of Fe-3d and N-2p states, the magnetic moment of Fe atoms decreases with an increase in the number of nearest neighbor nitrogen atoms. - Highlights: • Single phase γ′-Fe 4 N, ε-Fe 3−x N, and γ″-FeN films were obtained using dc sputtering. • The phases in iron nitride films can be controlled by the nitrogen partial pressure. • The nearest N neighbors have a significant influence on the exchange splitting of Fe

  6. Influence of the phase composition on the catalytic properties of ammonia synthesis catalysts

    International Nuclear Information System (INIS)

    Peev, T.M.; Bojinova, A.I.; Krylova, A.V.

    1981-01-01

    The phase composition of CA-1-type catalysts for ammonia synthesis was investigated by means of Moessbauer spectroscopy. A correlation was found between the catalytic activity of the samples and their wuestite content. (author)

  7. Microchannel Reactors for ISRU Applications Using Nanofabricated Catalysts, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Makel Engineering, Inc. (MEI) and USRA propose to develop microchannel reactors for In-Situ Resources Utilization (ISRU) using nanofabricated catalysts. The proposed...

  8. Additively Manufactured Monolithic Catalyst Bed for Green Propellants, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposal aims to develop a low cost, high efficiency catalyst technology to address navigation and maneuver difficulties in NASA's return missions. Our approach...

  9. Iron in carbonate containing AFm phases

    International Nuclear Information System (INIS)

    Dilnesa, B.Z.; Lothenbach, B.; Le Saout, G.; Renaudin, G.; Mesbah, A.; Filinchuk, Y.; Wichser, A.; Wieland, E.

    2011-01-01

    One of the AFm phases in hydrated Portland cement is Ca 3 (Al x Fe 2 - x )O 6 .CaCO 3 .nH 2 O. It is based on hexagonal and platey structural elements and the interlayer structure incorporates CO 3 2- . The solid phases were experimentally synthesized and characterized by different techniques including X-ray techniques (XRD and EXAFS) and vibrational spectroscopy techniques (IR, Raman). Fe-monocarbonate (Fe-Mc) and Al-monocarbonate (Al-Mc) were found to be stable up to 50 o C, while Fe-hemicarbonate (Fe-Hc) was unstable with respect to Fe-Mc in the presence of calcite. Fe-Mc has a rhombohedral R3-barc symmetry which is different from the triclinic of the Al analogue. Both XRD and thermodynamic modelling of the liquid compositions indicated that Al-Mc and the Fe-Mc phases do not form solid solution. The solubility products were calculated experimentally at 20 o C and 50 o C. Under standards condition the solubility products and other thermodynamic parameters were estimated using temperature-solubility product extrapolation and found to be logK S0 (Fe-Mc) = -34.59 ± 0.50, logK S0 (Fe-Hc) = -30.83 ± 0.50 and logK S0 (Al-Mc) = -31.32 ± 0.50.

  10. Synthesis of Acrolein from Glycerol Using FePO4 Catalyst in Liquid Phase Dehydration

    Directory of Open Access Journals (Sweden)

    Akhmad Zainal Abidin

    2016-02-01

    Full Text Available Acrolein is currently produced using propylene from crude oil while its price and scarcity are increasing. A renewable material such as glycerol is an attractive alternative for acrolein production. It can be obtained from crude palm oil (CPO and is a byproduct of biodiesel production. Besides being able to compete economically, glycerol is an environmentally friendly material. The purpose of this study is to synthesize acrolein from glycerol using FePO4 catalyst in liquid phase dehydration. The catalyst was prepared by three different methods: hydrothermal (catalyst A, deposition at Fe/P = 1.15 (catalyst B, and deposition at Fe/P = 1.20 (catalyst C. The experimental reaction temperature was varied at 220, 240 and 260 °C under constant atmospheric pressure. The results showed that catalyst C provided the best yield (91%, followed by catalyst A (90% and catalyst B (82%. The increasing reaction temperature showed a tendency to increase the yield of acrolein, while the presence of oxygen reduced the yield of acrolein and allowed the reaction to produce more side products such as glycerol propanal, acetaldehyde, and propionate. Catalyst reuse without any regeneration resulted in a yield profile of acrolein that continued to decline.

  11. Syntheses of organic compounds in the presence of the fused iron catalyst and their mechanisms and kinetics

    Science.gov (United States)

    Glebov, L. S.; Kliger, G. A.

    1989-10-01

    New synthetic possibilities of the reduced promoted fused iron catalyst in intermolecular and intramolecular amination, cyanation, hydrogenation-dehydrogenation, and hydrodeoxygenation reactions and intermolecular and intramolecular dehydration, polymerisation, and isotope exchange are examined. The mechanisms and kinetics of the reactions leading to the synthesis of amines, alcohols, hydrocarbons, and other organic compunds are discussed. A laser Raman spectroscopic method is described for the investigation of heterogeneous organic catalysis in situ. The bibliography includes 148 references.

  12. Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC

    Directory of Open Access Journals (Sweden)

    Mojca Rangus

    2014-05-01

    Full Text Available Iron-functionalized disordered mesoporous silica (FeKIL-2 is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM. We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05. From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1 the optimal concentration of stable isolated Fe3+ in the silica support; and (2 accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2 when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41.

  13. Iron Fischer-Tropsch Catalysts Prepared by Solvent-Deficient Precipitation (SDP: Effects of Washing, Promoter Addition Step, and Drying Temperature

    Directory of Open Access Journals (Sweden)

    Kyle M. Brunner

    2015-07-01

    Full Text Available A novel, solvent-deficient precipitation (SDP method for catalyst preparation in general and for preparation of iron FT catalysts in particular is reported. Eight catalysts using a 23 factorial design of experiments to identify the key preparation variables were prepared. The catalysts were characterized by electron microprobe, N2 adsorption, TEM, XRD, and ICP. Results show that the morphology of the catalysts, i.e., surface area, pore volume, pore size distribution, crystallite sizes, and promoter distribution are significantly influenced by (1 whether or not the precursor catalyst is washed, (2 the promoter addition step, and (3 the drying condition (temperature. Consequently, the activity, selectivity, and stability of the catalysts determined from fixed-bed testing are also affected by these three variables. Unwashed catalysts prepared by a one-step method and dried at 100 °C produced the most active catalysts for FT synthesis. The catalysts of this study prepared by SDP compared favorably in activity, productivity, and stability with Fe FT catalysts reported in the literature. It is believed that this facile SDP approach has promise for development of future FT catalysts, and also offers a potential alternate route for the preparation of other catalysts for various other applications.

  14. Effect of Support Pretreatment Temperature on the Performance of an Iron Fischer–Tropsch Catalyst Supported on Silica-Stabilized Alumina

    Directory of Open Access Journals (Sweden)

    Kamyar Keyvanloo

    2018-02-01

    Full Text Available The effect of support material pretreatment temperature, prior to adding the active phase and promoters, on Fischer–Tropsch activity and selectivity was explored. Four iron catalysts were prepared on silica-stabilized alumina (AlSi supports pretreated at 700 °C, 900 °C, 1100 °C or 1200 °C. Addition of 5% silica to alumina made the AlSi material hydrothermally stable, which enabled the unusually high support pretreatment temperatures (>900 °C to be studied. High-temperature dehydroxylation of the AlSi before impregnation greatly reduces FeO·Al2O3 surface spinel formation by removing most of the support-surface hydroxyl groups leading to more effectively carbided catalyst. The activity increases more than four-fold for the support calcined at elevated temperatures (1100–1200 °C compared with traditional support calcination temperatures of <900 °C. This unique pretreatment also facilitates the formation of ε′-Fe2.2C rather than χ-Fe2.5C on the AlSi support, which shows an excellent correlation with catalyst productivity.

  15. Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2014-01-01

    Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting...

  16. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    International Nuclear Information System (INIS)

    Zhou, Juan; Chen, Huan; Chen, Quanyuan; Huang, Zhaolu

    2016-01-01

    Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N 2 adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d 5/2 shifted to higher positions while that of Au 4f 7/2 had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest catalytic activity

  17. Bimetallic Au-decorated Pd catalyst for the liquid phase hydrodechlorination of 2,4-dichlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Juan [School of the Environment, Donghua University, Shanghai 201620 (China); Chen, Huan, E-mail: hchen404@njust.edu.cn [Key Laboratory of Jiangsu Province for Chemical Pollution Control and Resources Reuse, School of Environmental & Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Chen, Quanyuan; Huang, Zhaolu [School of the Environment, Donghua University, Shanghai 201620 (China)

    2016-11-30

    Graphical abstract: 2,4-Dichlorophenol can be converted to phenol via the catalytic HDC method over Pd-Au/CNTs and the catalytic activity first increased and then decreased with Au content. - Highlights: • Bimetallic catalysts had smaller metal particles and larger number of exposed active site than the monometallic catalysts. • The cationization of Pd particles increased with Au content in the bimetallic catalysts. • The bimetallic catalysts exhibited higher catalytic activities for HDC of 2,4-DCP than the monometallic counterparts. • The concerted pathway for HDC of 2,4-DCP was more predominant with increasing Au content in the bimetallic catalyst. - Abstract: Monometallic and bimetallic Pd-Au catalysts supported on multi-walled carbon nanotubes (CNTs) with varied Au cooperation amounts were prepared using the complexing-reduction method in the presence of tetrahydrofuran (THF). The liquid phase catalytic hydrodechlorination (HDC) of 2,4-dichlorophenol (2,4-DCP) was investigated over these bimetallic catalysts. The catalysts were characterized by N{sub 2} adsorption-desorption isotherms, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and H{sub 2} chemisorption. Characterization results showed that the co-reduction of Pd and Au mainly formed alloy-like structure. The bimetallic catalysts had smaller metal particles and larger numbers of exposed active site than that of monometallic catalysts. In addition, compared with Pd(1.7)/CNTs and Au(0.4)/CNTs, the binding energies of Pd 3d{sub 5/2} shifted to higher positions while that of Au 4f{sub 7/2} had negative shifts in the Pd-Au bimetallic catalysts, which can be ascribed to the electrons transferred from metal Pd to Au and the cationization of Pd particles was enhanced. Accordingly, the bimetallic Pd-Au particles with different Au contents in the catalysts exhibited varied synergistic effects for the catalytic HDC of 2,4-DCP, with Pd(1.8)Au(0.4)/CNTs having the highest

  18. Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts

    DEFF Research Database (Denmark)

    Riisager, Anders; Wasserscheid, Peter; Van Hal, R.

    2003-01-01

    Continuous flow gas-phase hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1-n-butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1-n-butyl...

  19. Black reefs: iron-induced phase shifts on coral reefs.

    Science.gov (United States)

    Kelly, Linda Wegley; Barott, Katie L; Dinsdale, Elizabeth; Friedlander, Alan M; Nosrat, Bahador; Obura, David; Sala, Enric; Sandin, Stuart A; Smith, Jennifer E; Vermeij, Mark J A; Williams, Gareth J; Willner, Dana; Rohwer, Forest

    2012-03-01

    The Line Islands are calcium carbonate coral reef platforms located in iron-poor regions of the central Pacific. Natural terrestrial run-off of iron is non-existent and aerial deposition is extremely low. However, a number of ship groundings have occurred on these atolls. The reefs surrounding the shipwreck debris are characterized by high benthic cover of turf algae, macroalgae, cyanobacterial mats and corallimorphs, as well as particulate-laden, cloudy water. These sites also have very low coral and crustose coralline algal cover and are call black reefs because of the dark-colored benthic community and reduced clarity of the overlying water column. Here we use a combination of benthic surveys, chemistry, metagenomics and microcosms to investigate if and how shipwrecks initiate and maintain black reefs. Comparative surveys show that the live coral cover was reduced from 40 to 60% to reefs on Millennium, Tabuaeran and Kingman. These three sites are relatively large (>0.75 km(2)). The phase shift occurs rapidly; the Kingman black reef formed within 3 years of the ship grounding. Iron concentrations in algae tissue from the Millennium black reef site were six times higher than in algae collected from reference sites. Metagenomic sequencing of the Millennium Atoll black reef-associated microbial community was enriched in iron-associated virulence genes and known pathogens. Microcosm experiments showed that corals were killed by black reef rubble through microbial activity. Together these results demonstrate that shipwrecks and their associated iron pose significant threats to coral reefs in iron-limited regions.

  20. Stability and kinetic studies of supported ionic liquid phase catalysts for hydroformylation of propene

    DEFF Research Database (Denmark)

    Riisager, Anders; Fehrmann, Rasmus; Haumann, Marco

    2005-01-01

    Supported ionic liquid phase (SILP) catalysts have been studied with regard to their long-term stability in the continuous gas-phase hydroformylation of propene. Kinetic data have been acquired by variation of temperature, pressure, syngas composition, substrate concentration, and residence time...

  1. Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II precursor

    Directory of Open Access Journals (Sweden)

    N.V. Nikolenko

    2018-03-01

    Full Text Available It was demonstrated that iron molybdate catalysts for methanol oxidation can be prepared using Fe(II as a precursor instead of Fe(III. This would allow for reduction of acidity of preparation solutions as well as elimination of Fe(III oxide impurities which are detrimental for the process selectivity. The system containing Fe(II and Mo(VI species in aqueous solution was investigated using UV–Vis spectroscopy. It was demonstrated that three types of chemical reactions occur in the Fe(II–Mo(VI system: (i formation of complexes between Fe(II and molybdate(VI ions, (ii inner sphere oxidation of coordinated Fe(II by Mo(VI and (iii decomposition of the Fe–Mo complexes to form scarcely soluble Fe(III molybdate, Mo(VI hydrous trioxide and molybdenum blue. Solid molybdoferrate(II prepared by interaction of Fe(II and Mo(VI in solution was characterized by EDXA, TGA, DTA and XRD and a scheme of its thermal evolution proposed. The iron molybdate catalyst prepared from Fe(II precursor was tested in methanol-to-formaldehyde oxidation in a continuous flow fixed-bed reactor to show similar activity and selectivity to the conventional catalyst prepared with the use of Fe(III.

  2. Gasification of brown coal and char with carbon dioxide in the presence of finely dispersed iron catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Asami, K.; Sears, P.; Furimsky, E.; Ohtsuka, Y. [Osaka City University, Osaka (Japan). Dept. of Applied Chemistry

    1996-05-01

    Gasification of brown coal and char with CO{sub 2} using iron catalysts precipitated from an aqueous solution of FeCl{sub 3} has been studied. When the pyrolyzed char is gasified in the temperature-programmed mode, the presence of the iron can lower the temperature giving the maximal rate of CO formation by 130-160 K, a larger lowering being observed at a higher loading in the range of {le} 3 wt% Fe. The specific rates of the isothermal gasification iron-bearing chars at 1173 and 1223 K increase with increasing char conversion, resulting in complete gasification within a short reaction time. Comparison of the initial rates of uncatalyzed and catalyzed gasification reveals that iron addition can lower the reaction temperature by 120 K. Moessbauer spectra show that the precipitation iron exists as fine FeOOH particles, which are reduced mainly to Fe{sub 3}C on charring at 1123 K. Most of the Fe{sub 3}C is transformed into {alpha}-Fe and {gamma}-Fe at the initial stage of gasification, and subsequently these species are oxidized to FeO and Fe{sub 3}O{sub 4}. The changes during gasification are discussed in terms of solid-gas and solid-solid reactions. 23 refs., 10 figs.

  3. Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

    Science.gov (United States)

    Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

    2018-03-01

    Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Visible-light Homogeneous Photocatalytic Conversion of CO2 into CO in Aqueous Solutions with an Iron Catalyst.

    Science.gov (United States)

    Rao, Heng; Bonin, Julien; Robert, Marc

    2017-11-23

    An iron-substituted tetraphenyl porphyrin bearing positively charged trimethylammonio groups at the para position of each phenyl ring catalyzes the photoinduced conversion of CO 2 . This complex is water soluble and acts as a molecular catalyst to selectively reduce CO 2 into CO under visible-light irradiation in aqueous solutions (acetonitrile/water=1:9 v/v) with the assistance of purpurin, a simple organic photosensitizer. CO is produced with a catalytic selectivity of 95 % and turnover number up to 120, illustrating the possibility of photocatalyzing the reduction of CO 2 in aqueous solution by using visible light, a simple organic sensitizer coupled to an amine as a sacrificial electron donor, and an earth-abundant metal-based molecular catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study

    Directory of Open Access Journals (Sweden)

    Basseem B. Hallac

    2018-02-01

    Full Text Available The extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt % lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe3O4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible light using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe2O3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe+2.57 for the catalyst with no lanthana and Fe+2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe+2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe+2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. The paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.

  6. Acrolein Production by Gas-Phase Glycerol Dehydration Using PO₄/Nb₂O5 Catalysts.

    Science.gov (United States)

    Lee, Kyu Am; Ryoo, HeeKyoung; Ma, Byung Chol; Kim, Youngchul

    2018-02-01

    In this study, modified niobium oxide were prepared to study the addictive effects on the catalytic performance for gas-phase glycerol dehydration. The catalysts were characterized by N2 adsorption/desorption, XRD, NH3-TPD, FT-IR. The amount of phosphoric acid was up to 50 wt% in niobium. As a result, the highest glycerol conversion was achieved over 20 wt% PO4/Nb2O5. It indicates that the optimal amount of phosphoric acid leads the catalyst to have appropriate acidity which is an important factor for gas-phase glycerol dehydration.

  7. Features of the kinetics of heterogeneous reactions with phase transformations on catalyst surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Berman, A D; Krylov, O V

    1978-01-01

    This paper presents a review of 41 bibliographic references to experiments on the adsorption of various gases (e.g., carbon monoxide, formic acid, ammonia, and oxygen) on metals (e.g., nickel, molybdenum, and platinum) and oxides covers observations of two-dimensional phases during adsorption; the kinetics of adsorption and catalysis associated with two-dimensional phase transitions; and several approximate models for describing the kinetics of heterogeneous catalysis which account for two-dimensional phase transformations on catalyst surfaces.

  8. Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

    Science.gov (United States)

    Kapoor, S; Sharma, P D; Gupta, Y K

    1975-09-01

    Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

  9. Catalyst Design Using Nanoporous Iron for the Chemical Vapor Deposition Synthesis of Single-Walled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Tarek M. Abdel-Fattah

    2013-01-01

    Full Text Available Single-walled carbon nanotubes (SWNTs have been synthesized via a novel chemical vapor deposition (CVD approach utilizing nanoporous, iron-supported catalysts. Stable aqueous dispersions of the CVD-grown nanotubes using an anionic surfactant were also obtained. The properties of the as-produced SWNTs were characterized through atomic force microscopy and Raman spectroscopy and compared with purified SWNTs produced via the high-pressure CO (HiPCO method as a reference, and the nanotubes were observed with greater lengths than those of similarly processed HiPCO SWNTs.

  10. Stability of the 1144 phase in iron pnictides

    Science.gov (United States)

    Song, B. Q.; Nguyen, Manh Cuong; Wang, C. Z.; Ho, K. M.

    2018-03-01

    A series of iron arsenides (e.g., CaRbFe4As4 , SrCsFe4As4 ) have been discovered recently, and have provoked a rise in superconductor searches in a different phase, known as the 1144 phase. For the presence of various chemical substitutions, it is believed that more 1144 compounds remain to be discovered. In this work, we perform general model analysis as well as scenario calculation on a basis of density functional theory to investigate phase stability in a variety of compounds. We predict that the 1144-type phase could be stabilized in EuKFe4As4 , EuRbFe4As4 , EuCsFe4As4 , CaCsFe4P4 , SrCsFe4P4 , BaCsFe4P4 , InCaFe4As4 , InSrFe4As4 , etc. Remarkably, it involves rare earths, trivalence elements (e.g., indium) and iron phosphides, which greatly expands the range of its existence and suggests a promising prospect for experimental synthesis. In addition, we find that the formation of many random doping compounds (e.g., Ba0.5Cs0.5Fe2As2 , Ba0.5Rb0.5Fe2As2 ) is driven by entropy and could be annealed to a 1144-type phase. Eventually, we plot a phase diagram about two structural factors Δ a and Δ c , giving a bird's-eye view of stability of various 1144 compounds.

  11. Mixed phase Pt-Ru catalyst for direct methanol fuel cell anode by flame aerosol synthesis

    DEFF Research Database (Denmark)

    Chakraborty, Debasish; Bischoff, H.; Chorkendorff, Ib

    2005-01-01

    A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst wa......Ru1/Vulcan carbon. The kinetics of methanol oxidation on the mixed phase catalyst was also explored by electrochemical impedance spectroscopy. (c) 2005 The Electrochemical Society.......A spray-flame aerosol catalyzation technique was studied for producing Pt-Ru anode electrodes for the direct methanol fuel cell. Catalysts were produced as aerosol nanoparticles in a spray-flame reactor and deposited directly as a thin layer on the gas diffusion layer. The as-prepared catalyst...... was found to be a mixture of nanocrystalline, mostly unalloyed Pt and an amorphous phase mostly of Ru and to a lesser extent of Pt oxides on top of the crystalline phase. The flame-produced Pt1Ru1 demonstrated similar onset potential but similar to 60% higher activity compared to commercially available Pt1...

  12. 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...

  13. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    Energy Technology Data Exchange (ETDEWEB)

    Peng, X.D.; Toseland, B.A.; Underwood, R.P. [Air Products and Chemicals, Inc., Allentown, PA (United States)

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  14. Removing organic contaminants with bifunctional iron modified rectorite as efficient adsorbent and visible light photo-Fenton catalyst

    International Nuclear Information System (INIS)

    Zhao, Xiaorong; Zhu, Lihua; Zhang, Yingying; Yan, Jingchun; Lu, Xiaohua; Huang, Yingping; Tang, Heqing

    2012-01-01

    Highlights: ► Rectorite was modified by ultrasonic-assisted ion-exchange and hydrolysis. ► The pillaring increased the layer-to-layer spacing of rectorite. ► The iron-modified rectorite was found to be an excellent adsorbent. ► The iron-modified rectorite showed good visible light photocatalytic ability. ► FeR was highly chemically stable with a wide operating range of pH. - Abstract: Iron-modified rectorite (FeR) was prepared as both adsorbent and catalyst. The iron modification increased layer-to-layer spacing and surface area of rectorite, leading to much increased adsorption of Rhodamine B (RhB) on rectorite. The maximum adsorption capacity of RhB on FeR reached 101 mg g −1 at pH 4.5, being 11 folds of that on the unmodified one. The iron modification also enabled rectorite to have efficient visible light photocatalytic ability. The apparent rate constant for the degradation of RhB (80 μM) at 298 K and pH 4.5 in the presence of H 2 O 2 (6.0 mM) and FeR (0.4 g L −1 ) was evaluated to be 0.0413 min −1 under visible light and 0.122 min −1 under sunlight, respectively. The analysis with electron spin resonance spin-trapping technique supported that the iron modified rectorite effectively catalyzed the decomposition of H 2 O 2 into hydroxyl radicals. On the basis of the characterization and analysis, the new bifunctional material was well clarified as both adsorbent and photocatalyst in the removing of organic pollutants.

  15. 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.

  16. Durability and regeneration of catalysts of the iron family in hydrogenation of low-temperature tar

    Energy Technology Data Exchange (ETDEWEB)

    Funasaka, W; Yokogawa, C; Hayashi, K; Kawamura, T; Fujita, H; Suga, S

    1949-01-01

    The low-temperature tar consisting of neutral and acidic oils has been reduced under atmospheric pressure between 400/sup 0/ and 500/sup 0/ by using catalysts prepared from Fe-Cr-kieselguhr, yellow ocher, and other material. When the reduction was performed at 480/sup 0/ with the yellow ocher from Niwasaka, Fukushima Prefacture, Japan, the low-temperature tar was easily converted to neutral and light oils and the catalysts could be regenerated by repeated baking and reduction. It is concluded that the commercialization of this reduction process is possible by using a cycle (each takes 20 minutes) composed of catalytic reaction, baking, and reduction of the catalysts.

  17. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama

    2016-09-29

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  18. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama; Alandini, Nurtalya; Rueping, Magnus

    2016-01-01

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  19. Mechanisms and modeling development of water transport/phase change in catalyst layers of portion exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Yexiang [Dept. of Thermal Engineering, Tsinghua University Beijing (China)], email: Yexiang.Xiao@energy.lth.se; Yuan, Jinliang; Sunden, Bengt [Dept. of Energy Sciences, Faculty of Engineering, Lund University (Sweden)], email: Jinliang.yuan@energy.lth.se, email: bengt.sunden@energy.lth.se

    2011-07-01

    Research on proton exchange membrane fuel cells has shown that incorporation of nanosized catalysts can effectively increase active areas and catalyst activity and make a great contribution to development in performance and catalyst utilization. Multiphase transport processes are as significant and complicated as water generation/transfer processes which occur in nano-structured catalyst layers. A review project has been launched aimed at gaining a comprehensive understanding of the mechanisms of water generation or transport phenomena. It covers catalytic reactions and water-phase change within the catalyst layers. The review proceeds in three main stages: Firstly, it characterizes and reconstructs the nano/micro-structured pores and solid-phases; secondly, it emphasises the importance of sensitive and consistent analysis of various water-phase change and transport schemes; and thirdly, it recommends development of microscopic models for multi-phase transport processes in the pores and the solid phases.

  20. Highly Selective Liquid-Phase Benzylation of Anisole with Solid-Acid Zeolite Catalysts

    DEFF Research Database (Denmark)

    Poreddy, Raju; Shunmugavel, Saravanamurugan; Riisager, Anders

    2015-01-01

    Zeolites were evaluated as solid acid catalysts for the liquid-phase benzylation of anisole with benzyl alcohol, benzyl bromide, and benzyl chloride at 80 °C. Among the examined zeolites, H-mordenite-10 (H-MOR-10) demonstrated particular high activity (>99 %) and excellent selectivity (>96...

  1. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    International Nuclear Information System (INIS)

    Shikada, T.; Fujimoto, K.; Tominaga, H.O.

    1986-01-01

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (175 0 C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac 2 O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  2. Supported liquid phase catalyst coating in micro flow Mizoroki-Heck reaction

    NARCIS (Netherlands)

    Stouten, S.C.; Noël, T.; Wang, Q.; Hessel, V.

    2015-01-01

    A Supported Liquid Phase Catalyst (SLPC) coating was successfully applied for the Mizoroki–Heck reaction in micro flow. Foremost, extended on stream operation was enabled and the on stream performance stability was verified. Stable catalytic activity was achieved during two consecutive runs totaling

  3. Operando Spectroscopy of the Gas-Phase Aldol Condensation of Propanal over Solid Base Catalysts

    NARCIS (Netherlands)

    Hernández-giménez, Ana M.; Ruiz-martínez, Javier; Puértolas, Begoña; Pérez-ramírez, Javier; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2017-01-01

    The gas-phase aldol condensation of propanal, taken as model for the aldehyde components in bio-oils, has been studied with a combined operando set-up allowing to perform FT-IR & UV–Vis diffuse reflectance spectroscopy (DRS) with on-line mass spectrometry (MS). The selected solid base catalysts, a

  4. 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...

  5. 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)

  6. 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)

  7. Functionalized Poly(propylene imine) Dendrimers as Novel Phase Transfer Catalyst in Supercritical Cabon Dioxide

    NARCIS (Netherlands)

    Goetheer, E.L.V.; Baars, M.W.P.L.; Broeke, van den L.J.P.; Meijer, E.W.; Keurentjes, J.T.F.

    2000-01-01

    Perfluoro-functionalized poly(propylene imine) dendrimers have been used as reactive extractants for anionic species and as phase transfer catalysts for two types of reactions. Different generations of dendrimers have been used for applications in carbon dioxide. First, the reactive extraction of

  8. Graphite-supported platinum catalysts: Effects of gas and aqueous phase treatments

    Energy Technology Data Exchange (ETDEWEB)

    Vleeming, J.H.; Kuster, B.F.M.; Marin, G.B. [Eindhoven Univ. of Technology (Netherlands)] [and others

    1997-03-01

    The effects on the platinum particle diameter and the available platinum surface area of a graphite-supported platinum catalyst resulting from pretreatments and from performing a selective oxidation reaction are investigated. In the gas phase considerable catalyst sintering occurs only in the presence of oxygen at 773 K due to extensive carbon burn-off, whereas in an aqueous phase platinum particle growth is limited upon oxidative treatment. A hydrogen treatment in aqueous phase at 363 K causes platinum particle growth, aggregate formation, and covering of metal sites. These phenomena become more important with increasing pH. Platinum particle growth and aggregate formation are attributed to platinum particle rather than platinum adatom mobility and is caused by the destruction of the oxygen-containing surface groups on the graphite support, which serve as anchorage sites for the platinum particles. Site covering is caused by products originating from the graphite support, which are formed as a result of the reductive treatments. When performing the aqueous phase oxidation of methyl {alpha}-D-glucopyranoside at 323 K and a pH of 9, catalyst modifications are small under oxidative conditions. Exposure of the catalyst for several hours to methyl {alpha}-D-glucopyranoside under the same conditions but in the absence of oxygen causes site covering. 50 refs., 9 figs., 1 tab.

  9. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie

    2014-01-01

    Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

  10. Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst.

    Science.gov (United States)

    Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2015-01-01

    Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.

  11. Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst

    Science.gov (United States)

    Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

    2015-01-01

    Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption. PMID:26517827

  12. Iron Phthalocyanine as New Efficient Catalyst for Catalytic Transfer Hydrogenation of Simple Aldehydes and Ketones

    Czech Academy of Sciences Publication Activity Database

    Bata, P.; Notheisz, F.; Klusoň, Petr; Zsigmond, A.

    2015-01-01

    Roč. 29, JAN 2015 (2015), s. 45-49 ISSN 0268-2605 Institutional support: RVO:67985858 Keywords : heterogenized complexes * catalytic transfer hydrogenation * reusable catalyst Subject RIV: CC - Organic Chemistry Impact factor: 2.452, year: 2015

  13. 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.

  14. Efficient degradation of phenol using iron-montmorillonite as a Fenton catalyst: Importance of visible light irradiation and intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Xipeng; Wu, Honghai, E-mail: wuhonghai@scnu.edu.cn; He, Guangping, E-mail: hegp@scnu.edu.cn; Guan, Yufeng

    2017-01-05

    Highlights: • Iron-montmorillonite has excellent catalytic activity on phenol Fenton degradation. • Phenol Fenton reaction follows the two-stage pseudo first order kinetic equations. • Role of visible light irradiation is more evident during induction reaction period. • Hydroquinone and catechol have a significant effect on the second-stage kinetics. - Abstract: Iron-montmorillonite (Fe-Mt) with delaminated structures was synthesized via the introduction of iron oxides into Na-montmorillonite. Fe-Mt showed significant increases in the available iron content, surface area and pore volume, along with a slight increase in the basal spacing from d{sub 001} = 1.26 (Na-Mt) to 1.53 nm (Fe-Mt). The Fenton process was efficient for phenol removal using Fe-Mt as a catalyst under visible light irradiation, and the process had two-stage pseudo-first order kinetics. The overall reaction had a higher degradation rate even when it was only irradiated with visible light for the first 40 min period. Further investigation confirmed that the irradiation increased the presence of certain intermediates. Among them, 1,4-benzoquinone, hydroquinone, and catechol all enhanced the Fenton reaction rates. Either catechol or hydroquinone was added to the Fenton system with Fe-Mt/H{sub 2}O{sub 2} with or without visible light irradiation, and they both accelerated phenol degradation because catechol and hydroquinone are capable of reductively and effectively transforming Fe(III) into Fe(II). The concentrations of dissolved total Fe increased with the increase in the oxalic acid concentration, which can strongly chelate Fe(III). Hence, iron was released from Fe-Mt, and reductive transformation played an important role in promoting the Fenton reaction process for phenol removal.

  15. Efficient degradation of phenol using iron-montmorillonite as a Fenton catalyst: Importance of visible light irradiation and intermediates

    International Nuclear Information System (INIS)

    Wei, Xipeng; Wu, Honghai; He, Guangping; Guan, Yufeng

    2017-01-01

    Highlights: • Iron-montmorillonite has excellent catalytic activity on phenol Fenton degradation. • Phenol Fenton reaction follows the two-stage pseudo first order kinetic equations. • Role of visible light irradiation is more evident during induction reaction period. • Hydroquinone and catechol have a significant effect on the second-stage kinetics. - Abstract: Iron-montmorillonite (Fe-Mt) with delaminated structures was synthesized via the introduction of iron oxides into Na-montmorillonite. Fe-Mt showed significant increases in the available iron content, surface area and pore volume, along with a slight increase in the basal spacing from d_0_0_1 = 1.26 (Na-Mt) to 1.53 nm (Fe-Mt). The Fenton process was efficient for phenol removal using Fe-Mt as a catalyst under visible light irradiation, and the process had two-stage pseudo-first order kinetics. The overall reaction had a higher degradation rate even when it was only irradiated with visible light for the first 40 min period. Further investigation confirmed that the irradiation increased the presence of certain intermediates. Among them, 1,4-benzoquinone, hydroquinone, and catechol all enhanced the Fenton reaction rates. Either catechol or hydroquinone was added to the Fenton system with Fe-Mt/H_2O_2 with or without visible light irradiation, and they both accelerated phenol degradation because catechol and hydroquinone are capable of reductively and effectively transforming Fe(III) into Fe(II). The concentrations of dissolved total Fe increased with the increase in the oxalic acid concentration, which can strongly chelate Fe(III). Hence, iron was released from Fe-Mt, and reductive transformation played an important role in promoting the Fenton reaction process for phenol removal.

  16. Synthesis and characterization of β-phase iron silicide nano-particles by chemical reduction

    International Nuclear Information System (INIS)

    Sen, Sabyasachi; Gogurla, Narendar; Banerji, Pallab; Guha, Prasanta K.; Pramanik, Panchanan

    2015-01-01

    Graphical abstract: - Highlights: • β-FeSi 2 nano-particle was synthesized by reducing with Mg and by diluting with MgO. • XRD profile shows the iron di-silicide phase to be semiconducting β-FeSi 2 . • HRTEM and FESEM images indicate the β-FeSi 2 average particle size to be 60–70 nm. • Absorption, reflectance and PL spectroscopy show band gap to be direct 0.87 eV. • Nano-β-FeSi 2 is p-type with hole density of 4.38 × 10 18 cm −3 and mobility 8.9 cm 2 /V s. - Abstract: Nano-particles of β-FeSi 2 have been synthesized by chemical reduction of a glassy phase of [Fe 2 O 3 , 4SiO 2 ] by Mg-metal where MgO is used as diluent to prevent the agglomeration of nano crystallites into micro-particles and also act as a negative catalyst for the formation of other phases. The sample is characterized by XRD, FESEM, HRTEM, EDX, ultra-violet-visible-infrared and PL spectroscopy and electronic properties have been investigated by Hall measurement. XRD profile shows that the synthesized powder consists of purely β-FeSi 2 semiconducting phase. The average crystallite size of β-FeSi 2 is determined to be around 65.4 nm from XRD peaks as well as from FESEM also. The optical absorption and PL spectroscopy shows that synthesized β-FeSi 2 phase is a direct band gap semiconductor with a value of 0.87 eV. Hall measurements show that β-FeSi 2 nano-particles is p-type with hole concentration of 4.38 × 10 18 cm −3 and average hole mobility of 8.9 cm 2 /V s at 300 K

  17. Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Heterogeneous Iron Catalysts.

    Science.gov (United States)

    Li, Jiang; Liu, Jun-Ling; Liu, He-Yang; Xu, Guang-Yue; Zhang, Jun-Jie; Liu, Jia-Xing; Zhou, Guang-Lin; Li, Qin; Xu, Zhi-Hao; Fu, Yao

    2017-04-10

    This work provided the first example of selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe-phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate-determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H-donors. The excellent stability of the Fe catalyst, which was probably a result of the well-preserved active species and the pore structure of the Fe catalyst in the presence of H 2 , was demonstrated in batch and continuous flow fixed-bed reactors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

    Science.gov (United States)

    Taninouchi, Yu-ki; Okabe, Toru H.

    2018-05-01

    The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

  19. Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)

    2017-09-26

    It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability

  20. WxC-β-SiC Nanocomposite Catalysts Used in Aqueous Phase Hydrogenation of Furfural

    Directory of Open Access Journals (Sweden)

    Jacek Rogowski

    2017-11-01

    Full Text Available This study investigates the effects of the addition of tungsten on the structure, phase composition, textural properties and activities of β-SiC-based catalysts in the aqueous phase hydrogenation of furfural. Carbothermal reduction of SiO2 in the presence of WO3 at 1550 °C in argon resulted in the formation of WxC-β-SiC nanocomposite powders with significant variations in particle morphology and content of WxC-tipped β-SiC nano-whiskers, as revealed by TEM and SEM-EDS. The specific surface area (SSA of the nanocomposite strongly depended on the amount of tungsten and had a notable impact on its catalytic properties for the production of furfuryl alcohol (FA and tetrahydrofurfuryl alcohol (THFA. Nanocomposite WxC-β-SiC catalysts with 10 wt % W in the starting mixture had the highest SSA and the smallest WxC crystallites. Some 10 wt % W nanocomposite catalysts demonstrated up to 90% yield of THFA, in particular in the reduction of furfural derived from biomass, although the reproducible performance of such catalysts has yet to be achieved.

  1. WxC-β-SiC Nanocomposite Catalysts Used in Aqueous Phase Hydrogenation of Furfural.

    Science.gov (United States)

    Rogowski, Jacek; Andrzejczuk, Mariusz; Berlowska, Joanna; Binczarski, Michal; Kregiel, Dorota; Kubiak, Andrzej; Modelska, Magdalena; Szubiakiewicz, Elzbieta; Stanishevsky, Andrei; Tomaszewska, Jolanta; Witonska, Izabela Alina

    2017-11-22

    This study investigates the effects of the addition of tungsten on the structure, phase composition, textural properties and activities of β-SiC-based catalysts in the aqueous phase hydrogenation of furfural. Carbothermal reduction of SiO₂ in the presence of WO₃ at 1550 °C in argon resulted in the formation of W x C-β-SiC nanocomposite powders with significant variations in particle morphology and content of W x C-tipped β-SiC nano-whiskers, as revealed by TEM and SEM-EDS. The specific surface area (SSA) of the nanocomposite strongly depended on the amount of tungsten and had a notable impact on its catalytic properties for the production of furfuryl alcohol (FA) and tetrahydrofurfuryl alcohol (THFA). Nanocomposite W x C-β-SiC catalysts with 10 wt % W in the starting mixture had the highest SSA and the smallest W x C crystallites. Some 10 wt % W nanocomposite catalysts demonstrated up to 90% yield of THFA, in particular in the reduction of furfural derived from biomass, although the reproducible performance of such catalysts has yet to be achieved.

  2. Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas

    NARCIS (Netherlands)

    Oschatz, M; van Deelen, T W; Weber, J L; Lamme, W S; Wang, G; Goderis, B; Verkinderen, O; Dugulan, A I; de Jong, K P

    2016-01-01

    Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon

  3. Synthesis of carbon nanotubes by CVD method using iron and molybdenum-based catalysts supported on ceramic matrices;Sintese de nanotubos de carbono por CVD utilizando catalisadores a base de ferro e molibdenio suportados em matrizes ceramicas

    Energy Technology Data Exchange (ETDEWEB)

    Teixeira, Ana Paula de Carvalho

    2010-07-01

    Molybdenum is known for its synergistic effect in the synthesis of carbon nanotubes (CNs) by chemical vapor deposition (CVD method). When added to typical catalysts like iron, nickel, and cobalt, even in small quantities, it is increases the yield of these nanostructures. The presence of Mo also has an influence on the type and number of CN walls formed. Although this effect is widely documented in the literature, there is not yet a consensus about the mechanism of action of molybdenum in catalytic systems. The objective of the present work is to study the influence of molybdenum on the catalytic activity of iron nanoparticle-based catalysts supported on magnesium oxide (Fe/MgO system) in the synthesis of carbon nanotubes by the CVD method. The Mo concentration was systematically varied from null to molar ratio values four times greater than the quantity of Fe, and the obtained material (catalysts and carbon nanotubes) were broadly characterized by different techniques. In order to also study the influence of the preparation method on the final composition of the catalytic system phases, the catalytic systems (Fe/MgO e FeMo{sub x}/MgO) were synthesized by two different methods: co-precipitation and impregnation. The greatest CN yields were observed for the catalysts prepared by coprecipitation. The difference was attributed to better dispersion of the Fe and Mo phases in the catalyst ceramic matrix. In the precipitation stage, it was observed the formation of layered double hydroxides whose concentration increased with the Mo content up to the ratio of Mo/Fe equal to 0.2. This phase is related to a better distribution of Fe and Mo in this concentration range. Another important characteristic observed is that the ceramic matrix is not inert. It can react both with Fe and Mo and form the iron solid solution in the magnesium oxide and the phases magnesium-ferrite (MgFe{sub 2}0{sub 4}) and magnesium molybdate (MgMo0{sub 4}). The MgFe{sub 2}0{sub 4} phase is observed in

  4. Facile and large-scale synthesis of high quality few-layered graphene nano-platelets via methane decomposition over unsupported iron family catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Awadallah, Ahmed E., E-mail: ahmedelsayed_epri@yahoo.com [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Aboul-Enein, Ateyya A. [Process Development Division, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Kandil, Usama F. [Petroleum Application Department, Egyptian Petroleum Research Institute, 11727 Cairo (Egypt); Taha, Mahmoud Reda [Department of Civil Engineering, University of New Mexico, Albuquerque, NM 87131 (United States)

    2017-04-15

    High quality few-layered graphene nano-platelets (GNPs) were successfully prepared via catalytic chemical vapor deposition of methane under ambient pressure using substrate-free unsupported iron, cobalt, and nickel metallic sheets as catalysts. The bulk catalysts were prepared via combustion method using citric acid as a fuel. Various analytical techniques, including high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), temperature programmed reduction (TPR) and Raman spectroscopy were employed to characterize the fresh and reduced catalysts and to identify the morphological structure of the as-grown GNPs. TEM images of the reduced metal catalysts showed that polycrystalline metallic sheets were easily produced after complete reduction of unsupported metal oxides. The data demonstrated that the formation of zero-valent metallic sheets could effectively promote the growth of GNPs on their surfaces. The unsupported Ni catalyst exhibits higher catalytic growth activity in terms of GNPs yield (254 wt%) compared with all other catalysts. Raman spectra and TEM results established that a few layers of GNPs with high crystallinity and good graphitization were produced. TGA results further demonstrated that the as-grown GNPs exhibit significantly higher thermal stability in air atmosphere compared with other synthesis methods. - Highlights: • Few-layered graphene nanoplatelets were prepared via methane catalytic decomposition. • Metallic sheets of iron group metals were used as novel catalysts. • The surfaces of metallic sheets were found to be very effective for GNPs growth. • The number of layers is dependent on the morphological structure of the catalysts. • The unsupported metallic Ni catalyst exhibited higher catalytic growth activity.

  5. Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

    International Nuclear Information System (INIS)

    Wu, Ke; Zheng, Mengjia; Han, Yuxiang; Xu, Zhaoyi; Zheng, Shourong

    2016-01-01

    Highlights: • Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO_2. • Pd/TiO_2 prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO_2, CeO_2, Al_2O_3 and SiO_2 were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N_2 adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO_2 was much smaller than those in im-Pd/TiO_2 and pd-Pd/TiO_2. Pd particle size of the dp-Pd/TiO_2 catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO_2 catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd loading amount, the Pd catalyst supported on TiO_2 exhibited a much higher catalytic activity

  6. Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Ke [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Mengjia [Kuang Yaming Honors School, Nanjing University, Nanjing 210023 (China); Han, Yuxiang [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Xu, Zhaoyi, E-mail: zhaoyixu@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China); Zheng, Shourong [State Key Laboratory of Pollution Control and Resource Reuse, Jiangsu Key Laboratory of Vehicle Emissions Control, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-07-15

    Highlights: • Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared. • Deposition-precipitation method resulted in positively charged smaller Pd particle. • Complete debromination of tetrabromobisphenol A could be achieved on Pd/TiO{sub 2}. • Pd/TiO{sub 2} prepared by the deposition-precipitation method was more active. - Abstract: Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO{sub 2}, CeO{sub 2}, Al{sub 2}O{sub 3} and SiO{sub 2} were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N{sub 2} adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO{sub 2} was much smaller than those in im-Pd/TiO{sub 2} and pd-Pd/TiO{sub 2}. Pd particle size of the dp-Pd/TiO{sub 2} catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO{sub 2} catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd

  7. Application of New Electrolyte Model to Phase Transfer Catalyst (PTC) Systems

    DEFF Research Database (Denmark)

    Hyung Kim, Sun; Anantpinijwatna, Amata; Kang, Jeong Won

    2015-01-01

    Abstract Phase transfer catalyst (PTC) is used to transfer the desirable active form of an anion from the aqueous phase to organic phase where the reaction occurs. One of major challenges for process design of the PTC system is to establish a reliable thermodynamic model capable of describing pha...... in PTC systems, thereby, extending the application range of the PTC-system model. The solubility of PTC in organic solvents, which is a key factor for strategy of PTC and solvent selection, has been calculated using the e-NRTL-SAC model....

  8. Magnetic properties of iron-based catalysts activated by various CO{sub 2} concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Lim, Jung Tae; Kim, Chul Sung [Kookmin University, Seoul (Korea, Republic of); Chun, Dong Hyun; Park, Ji Chan [Korea Institute of Energy Research, Daejeon (Korea, Republic of)

    2014-12-15

    Fresh catalyst samples of 100Fe/5.26Cu/4.76K/18.2SiO{sub 2} in part per weight were synthesized by using a combination of a co-precipitation technique and spray-drying method and were activated in situ by using syngas (H{sub 2}/CO/xCO{sub 2}) with different amounts of CO{sub 2} (x = 0.0, 0.5, 1.0, and 2.0). All activated catalyst samples showed similar XRD patterns, a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide, regardless of the CO{sub 2} contents. From the Moessbauer spectra, we also observed a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide in all activated catalyst samples. The main compound of the activated catalyst sample activated by using CO{sub 2}-free syngas (H{sub 2}/CO) was magnetic χ-carbide, and the main compound changed from χ-carbide to ferrihydrite with increasing CO{sub 2} concentration, confirmed by both, Moessbauer spectra and XRD pattern.

  9. Predictive Modelling of Phase-Transfer Catalyst Systems for Improved and Innovative Design

    DEFF Research Database (Denmark)

    Anantpinijwatna, Amata; Hyung Kim, Sun; Sales-Cruz, Mauricio

    2016-01-01

    Phase-transfer catalyst (PTC) systems contain two immiscible liquid phases with a heterogeneous PTC transferring active ion from one phase to the other for converting the reactant to the desired product, and in the process generating the inactive ion. This type of reacting systems is receiving...... increasing attention as a novel organic synthesis option due to its flexible and easier operation, higher production yield, and ability to eliminate expensive solvents, although, not eliminating the use of solvents. New mathematical models of the PTC system, which includes physical and chemical equilibrium......, reaction mechanism and unit operation has been developed. In the developed model, the PTC system is divided into four sub-systems of aqueous-organic solvent partition, inorganic salt in aqueous phase, PTC in aqueous phase, and PTC in aqueous phase. Each subsystem requires an appropriate thermodynamic model...

  10. Microstructure and structural phase transitions in iron-based superconductors

    International Nuclear Information System (INIS)

    Wang Zhen; Cai Yao; Yang Huai-Xin; Tian Huan-Fang; Wang Zhi-Wei; Ma Chao; Chen Zhen; Li Jian-Qi

    2013-01-01

    Crystal structures and microstructural features, such as structural phase transitions, defect structures, and chemical and structural inhomogeneities, are known to have profound effects on the physical properties of superconducting materials. Recently, many studies on the structural properties of Fe-based high-T c superconductors have been published. This review article will mainly focus on the typical microstructural features in samples that have been well characterized by physical measurements. (i) Certain common structural features are discussed, in particular, the crystal structural features for different superconducting families, the local structural distortions in the Fe 2 Pn 2 (Pn = P As, Sb) or Fe 2 Ch 2 (Ch = S, Se, Te) blocks, and the structural transformations in the 122 system. (ii) In FeTe(Se) (11 family), the superconductivity, chemical and structural inhomogeneities are investigated and discussed in correlation with superconductivity. (iii) In the K 0.8 Fe 1.6+x Se 2 system, we focus on the typical compounds with emphasis on the Fe-vacancy order and phase separations. The microstructural features in other superconducting materials are also briefly discussed. (topical review - iron-based high temperature superconductors)

  11. Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

    Directory of Open Access Journals (Sweden)

    Azhar Hashmi

    2016-09-01

    Full Text Available The hydroxypivaldehyde (HPA precursor intermediate for the synthesis of neopentyl glycol (NPG is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

  12. Cross-Aldol condensation of isobutyraldehyde and formaldehyde using phase transfer catalyst

    OpenAIRE

    Azhar Hashmi

    2016-01-01

    The hydroxypivaldehyde (HPA) precursor intermediate for the synthesis of neopentyl glycol (NPG) is prepared by novel cross Aldol condensation of isobutyraldehyde and formaldehyde at 20 °C using benzyltrimethylammonium hydroxide, a basic phase transfer catalyst. A feed mole ratio of 1.1:1.0:0.04 (isobutyraldehyde:formaldehyde:benzyltrimethylammonium hydroxide) afforded hydroxypivaldehyde as white solid in almost quantitative yield with ∼100% selectivity.

  13. Synthesis of Acrolein From Glycerol Using FePO4 Catalyst in Liquid Phase Dehydration

    OpenAIRE

    Abidin, Akhmad Zainal; Afandi, Rani Guslianti; Graha, Hafis Pratama Rendra

    2016-01-01

    Acrolein is currently produced using propylene from crude oil while its price and scarcity are increasing. A renewable material such as glycerol is an attractive alternative for acrolein production. It can be obtained from crude palm oil (CPO) and is a byproduct of biodiesel production. Besides being able to compete economically, glycerol is an environmentally friendly material. The purpose of this study is to synthesize acrolein from glycerol using FePO4 catalyst in liquid phase dehydration....

  14. Procedure for the preparation of catalysts for application in catalytic gas phase reactions

    International Nuclear Information System (INIS)

    1976-01-01

    The invention describes the preparation of catalysts to be used in catalytic reactions in the gaseous phase. The catalytic material is disposed at the surface of a ceramic or carbon substrate (av. particle size 0.1 μ - 0.5 cm, surface area smaller than 20 m 2 /g) by bombardment of the catalytic material (Pt, Rh, Pd, Ru, Os, Ir) with energetic ions (Ne, Ar, Kr, Xe) in the vicinity of the substrate in medium vacuum

  15. Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

    Science.gov (United States)

    Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

    2015-06-01

    Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

  16. Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R., E-mail: kvrchary@iict.res.in

    2014-08-01

    Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO{sub 3}) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH{sub 3} TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

  17. Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

    Science.gov (United States)

    Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

    2014-08-01

    Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

  18. Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

    International Nuclear Information System (INIS)

    Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan, Pethan N.; Kumar Balla, Putra; Chary Komandur, V.R.

    2014-01-01

    Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol–gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO 3 ) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV–vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH 3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

  19. Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

    International Nuclear Information System (INIS)

    Kim, Yong Tae; Park, Eun Duck; Jung, Kwang Deog

    2010-01-01

    The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. γ-Al 2 O 3 , SiO 2 -Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , AC, CeO 2 and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, N 2 -physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia (NH 3 - TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at 315 .deg. C among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/ZrO 2 and HSiW/SiO 2 -Al 2 O 3 showed the highest acrolein selectivity. In the case of HSiW/ZrO 2 , the initial catalytic activity was recovered after the removal of the accumulated carbon species at 550 .deg. C in the presence of oxygen

  20. Carbon-encapsulated nickel-iron nanoparticles supported on nickel foam as a catalyst electrode for urea electrolysis

    International Nuclear Information System (INIS)

    Wu, Mao-Sung; Jao, Chi-Yu; Chuang, Farn-Yih; Chen, Fang-Yi

    2017-01-01

    Highlights: • Electrochemical process can purify the urea-rich wastewater, producing hydrogen gas. • Carbon-encapsulated nickel iron nanoparticles (CE-NiFe) are prepared by pyrolysis. • An ultra-thin layer of CE-NiFe nanoparticles is attached to the 3D Ni foam. • CE-NiFe nanoparticles escalate both the urea electrolysis and hydrogen evolution. - Abstract: A cyanide-bridged bimetallic coordination polymer, nickel hexacyanoferrate, could be pyrolyzed to form carbon-encapsulated nickel-iron (CE-NiFe) nanoparticles. The formation of nitrogen-doped spherical carbon shell with ordered mesoporous structure prevented the structural damage of catalyst cores and allowed the migration and diffusion of electrolyte into the hollow carbon spheres. An ultra-thin layer of CE-NiFe nanoparticles could be tightly attached to the three-dimensional macroporous nickel foam (NF) by electrophoretic deposition. The CE-NiFe nanoparticles could lower the onset potential and increase the current density in anodic urea electrolysis and cathodic hydrogen production as compared with bare NF. Macroporous NF substrate was very useful for the urea electrolysis and hydrogen production, which allowed for fast transport of electron, electrolyte, and gas products. The superior electrocatalytic ability of CE-NiFe/NF electrode in urea oxidation and water reduction made it favorable for versatile applications such as water treatment, hydrogen generation, and fuel cells.

  1. Use of Pyrolyzed Iron Ethylenediaminetetraacetic Acid Modified Activated Carbon as Air–Cathode Catalyst in Microbial Fuel Cells

    KAUST Repository

    Xia, Xue

    2013-08-28

    Activated carbon (AC) is a cost-effective catalyst for the oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). To enhance the catalytic activity of AC cathodes, AC powders were pyrolyzed with iron ethylenediaminetetraacetic acid (FeEDTA) at a weight ratio of FeEDTA:AC = 0.2:1. MFCs with FeEDTA modified AC cathodes and a stainless steel mesh current collector produced a maximum power density of 1580 ± 80 mW/m2, which was 10% higher than that of plain AC cathodes (1440 ± 60 mW/m 2) and comparable to Pt cathodes (1550 ± 10 mW/m2). Further increases in the ratio of FeEDTA:AC resulted in a decrease in performance. The durability of AC-based cathodes was much better than Pt-catalyzed cathodes. After 4.5 months of operation, the maximum power density of Pt cathode MFCs was 50% lower than MFCs with the AC cathodes. Pyridinic nitrogen, quaternary nitrogen and iron species likely contributed to the increased activity of FeEDTA modified AC. These results show that pyrolyzing AC with FeEDTA is a cost-effective and durable way to increase the catalytic activity of AC. © 2013 American Chemical Society.

  2. Iron

    Science.gov (United States)

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  3. DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions

    Science.gov (United States)

    Stachurska, Patrycja; Kuterasiński, Łukasz; Dziedzicka, Anna; Górecka, Sylwia; Chmielarz, Lucjan; Łojewska, Joanna; Sitarz, Maciej

    2018-01-01

    Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes—classical ion exchange and the ultrasound modified ion-exchange method—were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C. PMID:29301370

  4. Characterization and parametrical study of Rh-TPPTS supported ionic liquid phase (SILP) catalysts for ethylene hydroformylation

    DEFF Research Database (Denmark)

    Hanh, Nguyen Thi Ha; Duc, Duc Truong; Thang, Vu Dao

    2012-01-01

    The supported ionic liquid phase (SILP) catalysis technology was applied to continuous, gas-phase hydroformylation of ethylene. Rh-TPPTS SILP catalysts with relatively low ionic liquid loading were shown to be stable and highly activity for ethylene hydroformylation. However, the catalytic activity......, BET surface area and pore morphology of the catalysts depended on the content of ionic liquid. Hence, catalysts with high ionic liquid loading content showed deactivation at high reaction temperatures, possibly caused by redistribution of ionic liquid out of the pores under these conditions. (C) 2012...

  5. Iron modified titanium–hafnium binary oxides as catalysts in total oxidation of ethyl acetate

    Czech Academy of Sciences Publication Activity Database

    Tsoncheva, T.; Ivanova, R.; Henych, Jiří; Velinov, N.; Kormunda, M.; Dimitrov, M.; Paneva, D.; Slušná, Michaela; Mitov, I.; Štengl, Václav

    2016-01-01

    Roč. 81, JUN (2016), s. 14-19 ISSN 1566-7367 R&D Projects: GA MŠk LM2015073 Institutional support: RVO:61388980 Keywords : Titania–hafnia binary oxide s * Iron modifications * Support effect * Ethyl acetate oxydation Subject RIV: CA - Inorganic Chemistry Impact factor: 3.330, year: 2016

  6. Simultaneous Production of Reduced Nitrogen Compounds and Hydrocarbons Using Amorphous Iron Silicate Smokes as a Catalyst

    Science.gov (United States)

    Nuth, Joseph A., III; Hill, Hugh G. M.

    2001-01-01

    Amorphous iron silicates efficiently catalyze formation of hydrocarbons and ammonia under conditions similar to that found in the solar nebula. Preliminary data and rates will be discussed, and much further experimentation is required. Additional information is contained in the original extended abstract.

  7. Hydrocarbon conversion with cracking catalyst having co-combustion promoters lanthanum and iron

    International Nuclear Information System (INIS)

    Csicsery, S.M.

    1979-01-01

    A composition useful in hydrocarbon conversion processes such as catalytic cracking comprises 0.05 to 10 weight percent lanthanum associated with a refractory support. The composition may also include 0.02 to 10 weight percent iron. The refractory support is a zeolitic crystalline aluminosilicate

  8. Moessbauer spectrometry study and metallography of paramagnetic phases from zirconium-iron system

    International Nuclear Information System (INIS)

    Freitas Brandao Bittencourt, C. de.

    1976-01-01

    Binary alloys of zirconium with 3 to 23% of iron by weight, were made by diffusion at 875 0 C of iron onto thin plates of zirconium. Moessbauer spectroscopy and optic metallography indicated the phases Zr 2 Fe and Zr 4 Fe, the bulk of which probably formed during the diffusion. These phases were confirmed by electron probe microanalysis. Moessbauer spectra showed quadrupole doublets with the same hyperfine interaction parameters in both phases, but with clearly distinct asymmetries. (author)

  9. Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

    KAUST Repository

    Della Monica, Francesco; Vummaleti, Sai V. C.; Buonerba, Antonio; Nisi, Assunta De; Monari, Magda; Milione, Stefano; Grassi, Alfonso; Cavallo, Luigi; Capacchione, Carmine

    2016-01-01

    A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Support effects in single atom iron catalysts on adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S)

    Science.gov (United States)

    Gao, Zhengyang; Yang, Weijie; Ding, Xunlei; Lv, Gang; Yan, Weiping

    2018-04-01

    The effects of support on gas adsorption is crucial for single atom catalysts design and optimization. To gain insight into support effects on gas adsorption characteristics, a comprehensive theoretical study was performed to investigate the adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S) by utilizing single atom iron catalysts with three graphene-based supports. The adsorption geometry, adsorption energy, electronic and magnetic properties of the adsorption system have been explored. Additionally, the support effects have been analyzed through d-band center and Fermi softness, and thermodynamic analysis has been performed to consider the effect of temperature on gas adsorption. The support effects have a remarkable influence on the adsorption characteristics of four types of toxic gases which is determined by the electronic structure of graphene-based support, and the electronic structure can be characterized by Fermi softness of catalysts. Fermi softness and uplift height of Fe atom could be good descriptors for the adsorption activity of single atom iron catalysts with graphene-based supports. The findings can lay a foundation for the further study of graphene-based support effects in single atom catalysts and provide a guideline for development and design of new graphene-based support materials utilizing the idea of Fermi softness.

  11. Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

    KAUST Repository

    Della Monica, Francesco

    2016-08-25

    A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5.

    Science.gov (United States)

    Iglesias, O; Fernández de Dios, M A; Pazos, M; Sanromán, M A

    2013-09-01

    This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80-100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.

  13. Magnetic properties of iron catalyst particles in HiPco single wall carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Bittová, Barbara; Poltierová Vejpravová, Jana; Kalbáč, Martin; Burianová, Simona; Mantlíková, A.; Daniš, S.; Doyle, S.

    2011-01-01

    Roč. 115, č. 35 (2011), s. 17303-17309 ISSN 1932-7447 R&D Projects: GA ČR GAP204/10/1677 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40400503 Keywords : metal catalyst particles * carbon nanotubes * superparamagnet * core - shell model * inter-particle interactions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.805, year: 2011 http://pubs.acs.org/doi/abs/10.1021/jp203365g

  14. The use of Moessbauer technique in the identification of iron phases in blood

    International Nuclear Information System (INIS)

    A-lArabi, Ibtisam Abdusalam

    2008-03-01

    In this work we used marabou's technique, x-diffraction techniques, and thermal analysis to identify iron phases in a number of different samples such as: prescription medicine used as iron supplement, a blood sample from a healthy person, a blood sample from a person with thalassemia, and a sample from the plant (Jirjeer). In spite of the diminishing amount of iron in all of these samples we were able to identify the phases of iron and their proportions. There were an agreement between the results of x-ray diffraction and Moessbauer on the presence of the compound (FeSO 4 .H 2 O) in the first sample. We calculated the average particle size of this sample to be 0.2 μm. The Moessbauer results of the second sample indicated the presence of two iron phases. One with parameters (ΔΕ Q =1.376 mm/s, δ=-0.17 mm/s) was assigned to oxygenated hemoglobin. The second with parameters (ΔΕ Q =1.371 mm/s, δ=0.41 mm/s) was assigned to non-oxygenated hemoglobin. In the results of the third sample there was no indication of the presence of ferric iron which is the form in which excess iron is stored in the red blood cells of thalassaemic blood. The results of the fourth sample indicated that iron is present in the plant sample in two different sites in the iron-sulfur protein molecule. thermal analysis results helped in determining the temperatures at which there was phase transformation of iron compounds molecule. thermal analysis results helped in determining the temperatures at which there was phase transformation of iron compounds. (author)

  15. One-pot aqueous phase catalytic conversion of sorbitol to gasoline over nickel catalyst

    International Nuclear Information System (INIS)

    Weng, Yujing; Qiu, Songbai; Xu, Ying; Ding, Mingyue; Chen, Lungang; Zhang, Qi; Ma, Longlong; Wang, Tiejun

    2015-01-01

    Highlights: • Directly production gasoline (C5–C12 alkanes) from biomass-derived sugar alcohol sorbitol. • Temperature of STG (553–593 K) was lower than that of traditional methanol to gasoline (MTG) (623–773 K). • Gasoline yield of 46.9% and C7–C12 hydrocarbons reached up to 45.5% in the gasoline products. - Abstract: The carbon chain extension and hydrodeoxygenation steps play critical roles in the high-energy-density hydrocarbons production. In this paper, a systematic study had been carried out to investigate one-pot aqueous phase catalytic conversion of sorbitol to gasoline (STG) over bifunctional Ni-based catalysts. Characterization technologies of N 2 physisorption, X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH 3 temperature-programmed desorption (NH 3 -TPD) were used to study the textural properties, phase compositions, acid behavior and morphologies of the catalysts. The catalytic performances were tested in a fixed bed reactor. It was found that the physically mixed Ni/HZSM-5 and Ni/silica-gel (mesoporous SG) catalyst realized the carbon chain extension and exhibited excellent performances on hydrodeoxygenation (HDO) reaction (46.9% of gasoline (C5–C12) yield and 45.5% of C7–C12 hydrocarbons in the gasoline products). Especially, the temperature of STG (553–593 K) was lower obviously than that of the traditional methanol to gasoline (MTG) process (623–773 K). It provided a novel transformation of sorbitol to long-chain alkanes by one-pot process over the bifunctional catalyst (Ni@HZSM-5/SG), wherein hydrodeoxygenation, ketonization and aldol condensation steps were integrated

  16. Black reefs: iron-induced phase shifts on coral reefs

    NARCIS (Netherlands)

    Wegley Kelly, L.; Barott, K.L.; Dinsdale, E.; Friedlander, A.M.; Nosrat, B.; Obura, D.; Sala, E.; Sandin, S.A.; Smith, J.E.; Vermeij, M.J.A.; Williams, G.J.; Willner, D.; Rohwer, F.

    2012-01-01

    The Line Islands are calcium carbonate coral reef platforms located in iron-poor regions of the central Pacific. Natural terrestrial run-off of iron is non-existent and aerial deposition is extremely low. However, a number of ship groundings have occurred on these atolls. The reefs surrounding the

  17. Design Criteria, Operating Conditions, and Nickel-Iron Hydroxide Catalyst Materials for Selective Seawater Electrolysis.

    Science.gov (United States)

    Dionigi, Fabio; Reier, Tobias; Pawolek, Zarina; Gliech, Manuel; Strasser, Peter

    2016-05-10

    Seawater is an abundant water resource on our planet and its direct electrolysis has the advantage that it would not compete with activities demanding fresh water. Oxygen selectivity is challenging when performing seawater electrolysis owing to competing chloride oxidation reactions. In this work we propose a design criterion based on thermodynamic and kinetic considerations that identifies alkaline conditions as preferable to obtain high selectivity for the oxygen evolution reaction. The criterion states that catalysts sustaining the desired operating current with an overpotential seawater-mimicking electrolyte. The catalyst was synthesized by a solvothermal method and the activity, surface redox chemistry, and stability were tested electrochemically in alkaline and near-neutral conditions (borate buffer at pH 9.2) and under both fresh seawater conditions. The Tafel slope at low current densities is not influenced by pH or presence of chloride. On the other hand, the addition of chloride ions has an influence in the temporal evolution of the nickel reduction peak and on both the activity and stability at high current densities at pH 9.2. Faradaic efficiency close to 100 % under the operating conditions predicted by our design criteria was proven using in situ electrochemical mass spectrometry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Chemically and geographically distinct solid-phase iron pools in the Southern Ocean

    CSIR Research Space (South Africa)

    Mtshali, TN

    2012-11-01

    Full Text Available Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation...

  19. Cobalt–iron nano catalysts supported on TiO{sub 2}–SiO{sub 2}: Characterization and catalytic performance in Fischer–Tropsch synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Feyzi, Mostafa, E-mail: Dalahoo2011@yahoo.com [Faculty of Chemistry, Razi University, P. O. Box: +98-67149, Kermanshah (Iran, Islamic Republic of); Yaghobi, Nakisa; Eslamimanesh, Vahid [Iran Polymer and Petrochemical Institute, P. O. Box: +98- 14965 Tehran, Iran, (Iran, Islamic Republic of)

    2015-12-15

    Graphical abstract: The Co–Fe/TiO{sub 2}–SiO{sub 2} catalysts were prepared. The prepared catalysts were tested for light olefins and C{sub 5}–C{sub 12} production. The best operational conditions are 250 °C, H{sub 2}/CO = 1/1 under 5 bar pressure. - Highlights: • The TiO{sub 2}–SiO{sub 2} supported cobalt–iron catalysts were prepared via sol–gel method. • The best operational conditions were 250 °C, GHSV = 2000 h{sup −1}, H{sub 2}/CO = 1/1 and 5 bar. • The (Co/Fe)/TiO{sub 2}–SiO{sub 2} is efficient catalyst for light olefins and C{sub 5}–C{sub 12} production. - Abstract: A series of Co–Fe catalysts supported on TiO{sub 2}–SiO{sub 2} were prepared by the sol–gel method. This research investigated the effects of (Co/Fe) wt.%, the solution pH, different Co/Fe molar ratio, calcination conditions and different promoters on the catalytic performance of cobalt–iron catalysts for the Fisher–Tropsch synthesis (FTS). It was found that the catalyst containing 35 wt.% (Co–Fe)/TiO{sub 2}–SiO{sub 2} (Co/Fe molar ratio is 80/20) promoted with 1.5 wt.% Cu and calcined in air atmosphere at 600 °C for 7 h with a heating rate of 3 °C min{sup −1} is an optimal nano catalyst for converting synthesis gas to light olefins and C{sub 5}–C{sub 12} hydrocarbons. The effects of operational conditions such as the H{sub 2}/CO ratio, gas hourly space velocity (GHSV), different reaction temperature, and reaction pressure were investigated. The results showed that the best operational conditions for optimal nano catalyst are 250 °C, GHSV = 2000 h{sup −1}, H{sub 2}/CO molar ratio 1/1 under 5 bar total pressure. Catalysts and precursors were characterized by, X-ray diffraction (XRD), scanning electron microcopy (SEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature program reduction (TPR) and N{sub 2} adsorption–desorption measurements.

  20. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Directory of Open Access Journals (Sweden)

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  1. High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ping; Barkholtz, Heather M.; Wang, Ying; Xu, Weilin; Liu, Dijia; Zhuang, Lin

    2017-12-01

    We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.

  2. Uniformly active phase loaded selective catalytic reduction catalysts (V_2O_5/TNTs) with superior alkaline resistance performance

    International Nuclear Information System (INIS)

    Wang, Haiqiang; Wang, Penglu; Chen, Xiongbo; Wu, Zhongbiao

    2017-01-01

    Highlights: • VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3. • Ion-exchange reaction occurs between VOSO_4 and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO_4-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH_4VO_3 and VOSO_4) were used to synthesize deNO_x catalysts. The results showed that VOSO_4 exhibited better synergistic effect with titanate nanotubes than NH_4VO_3, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V"5"+/V"4"+ redox cycles and superior oxygen mobility were achieved. Besides, VOSO_4-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V_2O_5/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

  3. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    OpenAIRE

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, P. (Petra); Filip, P. (Petr); Vesel, A.

    2011-01-01

    The aim of this paper is to document suitability of plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids. Surface-modified carbonyl iron particles were prepared via their exposure to 50% argon and 50% octafluorocyclobutane plasma. The X-ray photoelectron spectroscopy was used for analysis of chemical bonding states in the surface layer. Plasma-treated particles were adopted for a dispersed phase in magnetorheological (MR) fluids, and the MR behaviour was in...

  4. Chemically and geographically distinct solid-phase iron pools in the Southern Ocean.

    Science.gov (United States)

    von der Heyden, B P; Roychoudhury, A N; Mtshali, T N; Tyliszczak, T; Myneni, S C B

    2012-11-30

    Iron is a limiting nutrient in many parts of the oceans, including the unproductive regions of the Southern Ocean. Although the dominant fraction of the marine iron pool occurs in the form of solid-phase particles, its chemical speciation and mineralogy are challenging to characterize on a regional scale. We describe a diverse array of iron particles, ranging from 20 to 700 nanometers in diameter, in the waters of the Southern Ocean euphotic zone. Distinct variations in the oxidation state and composition of these iron particles exist between the coasts of South Africa and Antarctica, with different iron pools occurring in different frontal zones. These speciation variations can result in solubility differences that may affect the production of bioavailable dissolved iron.

  5. Liquid Phase Plasma Synthesis of Iron Oxide/Carbon Composite as Dielectric Material for Capacitor

    Directory of Open Access Journals (Sweden)

    Heon Lee

    2014-01-01

    Full Text Available Iron oxide/carbon composite was synthesized using a liquid phase plasma process to be used as the electrode of supercapacitor. Spherical iron oxide nanoparticles with the size of 5~10 nm were dispersed uniformly on carbon powder surface. The specific capacitance of the composite increased with increasing quantity of iron oxide precipitate on the carbon powder up to a certain quantity. When the quantity of the iron oxide precipitate exceeds the threshold, however, the specific capacitance was rather reduced by the addition of precipitate. The iron oxide/carbon composite containing an optimum quantity (0.33 atomic % of iron oxide precipitate exhibited the smallest resistance and the largest initial resistance slope.

  6. Synergistic effect of iron and intumescent flame retardant on shape-stabilized phase change material

    International Nuclear Information System (INIS)

    Zhang Ping; Hu Yuan; Song Lei; Lu Hongdian; Wang Jian; Liu Qingqing

    2009-01-01

    This paper deals with the preparation of paraffin/high density polyethylene (HDPE)/intumescent flame retardant (IFR)/iron as flame retardant shape-stabilized phase change material (FSPCM). The influences of iron for FSPCM on morphology, flammability property, latent heat and thermal conductive property were characterized by scanning electron microscopy (SEM), cone calorimeter, differential scanning calorimetry (DSC) and hot disk thermal constants analyser. It was found that iron could be well dispersed into the composite formed by HDPE and paraffin; the flame retardant efficiency of IFR could be improved by adding iron; the thermal conductivity of FSPCM could be increased due to the high thermal conductivity of iron. At the same time, the possible flame retardant mechanism for paraffin/HDPE/IFR with iron as a FSPCM was proposed

  7. Identification of the iron oxidation state and coordination geometry in iron oxide- and zeolite-based catalysts using pre-edge XAS analysis.

    Science.gov (United States)

    Boubnov, Alexey; Lichtenberg, Henning; Mangold, Stefan; Grunwaldt, Jan Dierk

    2015-03-01

    Analysis of the oxidation state and coordination geometry using pre-edge analysis is attractive for heterogeneous catalysis and materials science, especially for in situ and time-resolved studies or highly diluted systems. In the present study, focus is laid on iron-based catalysts. First a systematic investigation of the pre-edge region of the Fe K-edge using staurolite, FePO4, FeO and α-Fe2O3 as reference compounds for tetrahedral Fe(2+), tetrahedral Fe(3+), octahedral Fe(2+) and octahedral Fe(3+), respectively, is reported. In particular, high-resolution and conventional X-ray absorption spectra are compared, considering that in heterogeneous catalysis and material science a compromise between high-quality spectroscopic data acquisition and simultaneous analysis of functional properties is required. Results, which were obtained from reference spectra acquired with different resolution and quality, demonstrate that this analysis is also applicable to conventionally recorded pre-edge data. For this purpose, subtraction of the edge onset is preferentially carried out using an arctangent and a first-degree polynomial, independent of the resolution and quality of the data. For both standard and high-resolution data, multiplet analysis of pre-edge features has limitations due to weak transitions that cannot be identified. On the other hand, an arbitrary empirical peak fitting assists the analysis in that non-local transitions can be isolated. The analysis of the oxidation state and coordination geometry of the Fe sites using a variogram-based method is shown to be effective for standard-resolution data and leads to the same results as for high-resolution spectra. This method, validated by analysing spectra of reference compounds and their well defined mixtures, is finally applied to track structural changes in a 1% Fe/Al2O3 and a 0.5% Fe/BEA zeolite catalyst during reduction in 5% H2/He. The results, hardly accessible by other techniques, show that Fe(3+) is

  8. Vanadium Influence on Iron Based Intermetallic Phases in AlSi6Cu4 Alloy

    Directory of Open Access Journals (Sweden)

    Bolibruchová D.

    2014-10-01

    Full Text Available Negative effect of iron in Al-Si alloys mostly refers with iron based intermetallic phases, especially Al5FeSi phases. These phases are present in platelet-like forms, which sharp edges are considered as main cracks initiators and also as contributors of porosity formation. In recent times, addition of some elements, for example Mn, Co, Cr, Ni, V, is used to reduce influence of iron. Influence of vanadium in aluminium AlSi6Cu4 alloy with intentionally increased iron content is presented in this article. Vanadium amount has been graduated and chemical composition of alloy has been analysed by spectral analysis. Vanadium influence on microstructural changes was evaluated by microstructural analysis and some of intermetallic particles were reviewed by EDX analysis.

  9. Lignite air-steam gasification in the fluidized bed of iron-containing slag catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, B.N.; Shchipko, M.L.; Golovin, Yu. [Inst. of Chemistry of Natural Organic Materials, Academgorodok, Krasnoyarsk (Russian Federation)

    1995-12-01

    The influence of fluidized bed of iron-containing slag particles on air-steam gasification of powdered Kansk-Achinsk lignite in entrained flow was studied in pilot installation with productivity about 60 kg per hour. Slag of Martin process and boiler slag were used as catalytic active materials until their complete mechanical attrition. Two following methods of catalytic gasification of lignite were compared: the partial gasification in stationary fluidized bed of slag particles with degree of fuel conversion 40-70% and complete gasification in circulating bed of slag particles. In the first case only the most reactive part of fuel is gasified with the simultaneously formation of porous carbon residue with good sorption ability. It was found the catalytic fluidized bed improves heat transfer from combustion to reduction zone of gas-generator and increases the rate of fuel conversion at the temperature range 900-1000{degrees}C. At these temperatures the degree of conversion is depended considerably on the duration time of fuel particles in the catalytic fluidized bed. The influence of catalytic fluidized bed height and velocity of reaction mixture on the temperature profiles in the gas-generator was studied. The optimal relationship was found between the fluidized bed height and velocity of flow which makes possible to produce the gas with higher calorific value at maximum degree of fuel conversion.

  10. Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment

    International Nuclear Information System (INIS)

    Liu, Xing-Wu; Cao, Zhi; Zhao, Shu; Gao, Rui

    2017-01-01

    As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2 C and ε’-Fe 2.2 C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe x C, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectra for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2 C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2 C has six sets of chemically distinct Fe atoms.

  11. Continuous gas-phase hydroformylation of 1-butene using supported ionic liquid phase (SILP) catalysts

    DEFF Research Database (Denmark)

    Haumann, Marco; Dentler, Katharina; Joni, Joni

    2007-01-01

    The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C8H17OSO3] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed...

  12. Preparation of iron boride layers from the gas phase

    International Nuclear Information System (INIS)

    Marx, G.; Plaenitz, H.; Treffer, G.; Koenig, H.; Altenburger, S.

    1980-01-01

    Coating of Armco iron, steel-C100W1, and steel-100Cr6 with borides by decomposition of boron tribromide on the surface of the specimens is described. The experiments were carried out in a laboratory apparatus at temperatures between 923 and 1223 K. The dependence of the thickness of the boride layers on time and temperature is presented in graphs

  13. Phase diagram and gap anisotropy in iron-pnictide superconductors

    Czech Academy of Sciences Publication Activity Database

    Ikeda, H.; Arita, R.; Kuneš, Jan

    2010-01-01

    Roč. 81, č. 5 (2010), 054502//1-054502//15 ISSN 1098-0121 Institutional research plan: CEZ:AV0Z10100521 Keywords : iron pnictides * superconductivity * fluctuation-exchange approximation Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.772, year: 2010 http://prb.aps.org/abstract/PRB/v81/i5/e054502

  14. Heterogeneous electro-Fenton using modified iron-carbon as catalyst for 2,4-dichlorophenol degradation: influence factors, mechanism and degradation pathway.

    Science.gov (United States)

    Zhang, Chao; Zhou, Minghua; Ren, Gengbo; Yu, Xinmin; Ma, Liang; Yang, Jie; Yu, Fangke

    2015-03-01

    Modified iron-carbon with polytetrafluoroethylene (PTFE) was firstly investigated as heterogeneous electro-Fenton (EF) catalyst for 2,4-dichlorophenol (2,4-DCP) degradation in near neutral pH condition. The catalyst was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), and the effects of some important operating parameters such as current intensity and pH on the 2,4-DCP degradation were investigated. After the catalyst modification with 20% PTFE, the degradation performance maintained well with much lower iron leaching, and at current intensity 100 mA, initial pH 6.7, catalyst loading 6 g/L, the degradation efficiency of 2,4-DCP could exceed 95% within 120 min treatment. Two-stage pseudo first-order kinetics of 2,4-DCP degradation was observed, including a slow anodic oxidation stage (first-stage) and much faster heterogeneous EF oxidation (second-stage), in which the automatic drop of pH in the first-stage initiated the Fe(2+) release from micro-electrolysis and thus benefited to the subsequent EF reaction. Aromatic intermediates such as 3,5-dichlorocatechol, 4,6-dichlororesorcinol and 2-chlorohydroquinone were detected by GC-MS. Oxalic acid, acetic acid, formic acid and Cl(-) were quantified by ion chromatograph. Based on these analysis as well as the detection of H₂O₂ and OH, a possible mechanism and degradation pathway for 2,4-DCP were proposed. This work demonstrated that such a heterogeneous EF using cheap modified Fe-C catalyst was promising for organic wastewater treatment in initial neutral pH condition. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Liu, Ying; Wu, Yan-Ying; Lv, Guo-Jun; Pu, Tao; He, Xing-Quan; Cui, Li-Li

    2013-01-01

    Graphical abstract: The fabricated FePc-Gr catalyst for ORR exhibited high activity, favoring a direct 4-electron process, good stability and selectivity, all of which should be attributed to its high conductivity, the synergistic effect between FePc and graphene, as well as the formation of stable FePc-Gr composite through covalent bonding and π–π interaction. - Abstract: A novel iron(II) phthalocyanine covalently modified graphene (FePc-Gr) was synthesized by reduction of the product obtained through an amidation reaction between carboxyl-functionalized graphene oxide (CFGO) and iron(II) tetra-aminophthalocyanine (FeTAPc). The FePc-Gr hybird was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic properties of FePc-Gr toward the oxygen reduction reaction (ORR) were evaluated using cyclic voltammetry (CV) and linear sweep voltammetry methods. The peak potential of the ORR on the FePc-Gr catalyst was found to be about −0.12 V vs. SCE in 0.1 M NaOH solution, which was 180 and 360 mV more positive than that on FeTAPc and bare GCE, respectively. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements revealed that the ORR mechanism was nearly via a direct four-electron pathway to water on FePc-Gr. The current still remained 83.5% of its initial after chronoamperometric test for 10,000 s. Nevertheless, Pt/C catalyst only retained 40.5% of its initial current. The peak potential and peak current changed slightly when 3 M methanol was introduced. So the FePc-Gr composite catalyst for ORR exhibited high activity, good stability and methanol-tolerance, which could be used as a promising Pt-free catalyst for ORR in alkaline direct methanol fuel cell (DMFC)

  16. Carbon in condensed hydrocarbon phases, steels and cast irons

    Directory of Open Access Journals (Sweden)

    GAFAROVA Victoria Alexandrovna

    2017-11-01

    Full Text Available The article presents a review of studies carried out mainly by the researchers of the Ufa State Petroleum Technological University, which are aimed at detection of new properties of carbon in such condensed media as petroleum and coal pitches, steels and cast irons. Carbon plays an important role in the industry of construction materials being a component of road and roof bitumen and setting the main mechanical properties of steels. It was determined that crystal-like structures appear in classical glass-like substances – pitches which contain several thousands of individual hydrocarbons of various compositions. That significantly extends the concept of crystallinity. In structures of pitches, the control parameter of the staged structuring process is paramagnetism of condensed aromatic hydrocarbons. Fullerenes were detected in steels and cast irons and identified by various methods of spectrometry and microscopy. Fullerene С60, which contains 60 carbon atoms, has diameter of 0,7 nm and is referred to the nanoscale objects, which have a significant influence on the formation of steel and cast iron properties. It was shown that fullerenes appear at all stages of manufacture of cast irons; they are formed during introduction of carbon from the outside, during crystallization of metal in welded joints. Creation of modified fullerene layers in steels makes it possible to improve anticorrosion and tribological properties of structural materials. At the same time, outside diffusion of carbon from the carbon deposits on the metal surface also leads to formation of additional amount of fullerenes. This creates conditions for occurrence of local microdistortions of the structure, which lead to occurrence of cracks. Distribution of fullerenes in iron matrix is difficult to study as the method is labor-intensive, it requires dissolution of the matrix in the hydrofluoric acid and stage fullerene separation with further identification by spectral methods.

  17. Numerical modeling of coupled heat transfer and phase transformation for solidification of the gray cast iron

    DEFF Research Database (Denmark)

    Jabbari, Masoud; Hosseinzadeh, Azin

    2013-01-01

    In the present study the numerical model in 2D is used to study the solidification bahavior of the gray cast iron. The conventional heat transfer is coupled with the proposed micro-model to predict the amount of different phases, i.e. total austenite (c) phase, graphite (G) and cementite (C...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-01

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

  19. Reduction of Furfural to Furfuryl Alcohol in Liquid Phase over a Biochar-Supported Platinum Catalyst

    Directory of Open Access Journals (Sweden)

    Ariadna Fuente-Hernández

    2017-02-01

    Full Text Available In this work, the liquid phase hydrogenation of furfural has been studied using a biochar-supported platinum catalyst in a batch reactor. Reactions were performed between 170 °C and 320 °C, using 3 wt % and 5 wt % of Pt supported on a maple-based biochar under hydrogen pressure varying from 500 psi to 1500 psi for reaction times between 1 h and 6 h in various solvents. Under all reactive conditions, furfural conversion was significant, whilst under specific conditions furfuryl alcohol (FA was obtained in most cases as the main product showing a selectivity around 80%. Other products as methylfuran (MF, furan, and trace of tetrahydrofuran (THF were detected. Results showed that the most efficient reaction conditions involved a 3% Pt load on biochar and operations for 2 h at 210 °C and 1500 psi using toluene as solvent. When used repetitively, the catalyst showed deactivation although only a slight variation in selectivity toward FA at the optimal experimental conditions was observed.

  20. Propene and l-octene hydroformylation with silica-supported, ionic liquid-phase (SILP) Rh-phosphine catalysts in continuous fixed-bed mode

    DEFF Research Database (Denmark)

    Riisager, Anders; Eriksen, Kim Michael; Wasserscheid, Peter

    2003-01-01

    - and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h(-1) for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.......Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium) phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM] [PF6], on a silica support. The catalysts were active in continuous gas...

  1. Iron-bearing phases in a peat-derived duricrust from Brazil

    OpenAIRE

    Varajao, Afdc; Da Costa, G. M.; Varajao, C. A. C.; Meunier, J. D.; Colin, Fabrice

    2007-01-01

    The formation of aluminium-substituted iron-minerals is still subject to debate. We report a case study in a Humic Gleysol soil profile, developed on a sedimentary saprolite, from a basin floor on the Uberaba Plateau (Minas Gerais State, Brazil) where iron-phases are crystallized by a ferruginization process. The mineralogical and chemical properties were investigated by X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry and Mossbauer spectroscopy. The specific s...

  2. Surface Termination of M1 Phase and Rational Design of Propane Ammoxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Guliants, Vadim [Univ. of Cincinnati, OH (United States)

    2015-02-16

    This final report describes major accomplishments in this research project which has demonstrated that the M1 phase is the only crystalline phase required for propane ammoxidation to acrylonitrile and that a surface monolayer terminating the ab planes of the M1 phase is responsible for their activity and selectivity in this reaction. Fundamental studies of the topmost surface chemistry and mechanism of propane ammoxidation over the Mo-V-(Te,Sb)-(Nb,Ta)-O M1 and M2 phases resulted in the development of quantitative understanding of the surface molecular structure – reactivity relationships for this unique catalytic system. These oxides possess unique catalytic properties among mixed metal oxides, because they selectively catalyze three alkane transformation reactions, namely propane ammoxidation to acrylonitrile, propane oxidation to acrylic acid and ethane oxidative dehydrogenation, all of considerable economic significance. Therefore, the larger goal of this research was to expand this catalysis to other alkanes of commercial interest, and more broadly, demonstrate successful approaches to rational design of improved catalysts that can be applied to other selective (amm)oxidation processes.

  3. X-ray diffraction study of phase transitions in iron(II) trisnioximate hexadecylboronate clathrochelate complex

    International Nuclear Information System (INIS)

    Vorontsov, I.I.; Antipin, M.Yu.; Dubovik, I.I.; Papkov, V.S.; Potekhin, K.A.; Voloshin, Ya.Z.; Stash, A.I.; Belsky, V.K.

    2001-01-01

    Crystals of the iron(II) nioximate hexadecylboronate clathrochelate complex-FeNx 3 (BHd ) 2 [tris(μ-1,2-cyclohexanedionedioximato-O:O ' )di-n-hexadecyldiborato(2-) - N,'''N''',N''',N''',N''',N ' ]iron(II) - are investigated by differential scanning calorimetry and X-ray diffraction. Two structural phase transitions are revealed at T cr1 = 290(3) K and T cr2 = 190(3) K. The crystal structures of phases I, II, and III are determined by X-ray diffraction analysis at 303, 243, and 153 K, respectively. It is demonstrated that the I ↔ II phase transition is due to a change in the system of translations, and the II ↔ III phase transition is accompanied only by a jumpwise change in the unit cell parameters. The possible mechanisms of phase transitions are discussed in terms of geometry and molecular packing of FeNx 3 (BHd) 2 in all three phases

  4. Gas-phase Hydrogenation of Crotonaldehyde Over Nickel-on-Kieselguhr Catalyst Pellets

    International Nuclear Information System (INIS)

    Uraz, C.; Atalay, F.; Atalay, S.

    2001-01-01

    Gas phase catalytic hydrogenation of crotonaldehyde to η-butanol was investigated. A nickel based commercial catalyst produced by Harshaw was used at constant temperatures ranging from 160 to 210deg; at pressures of 1.5, 2 , and 2.5 atm and at different crotonaldehyde to hydrogen feed ratios changing from 0.134 to 0.226. The conversion of crotonaldehyde at different operating conditions were determined and the reaction rates were calculated . The experimental results were fitted to ten langmuir-Hinshelwood/ Eley Rideal type models in addition to a homogeneous kinetics modal and the best modal was identified. The effects of external and internal mass transfer resistances were found to be negligible .(authors) refs 28., 2 figs , 4 tabs

  5. Particle Size and Crystal Phase Effects in Fischer-Tropsch Catalysts

    Directory of Open Access Journals (Sweden)

    Jin-Xun Liu

    2017-08-01

    Full Text Available Fischer-Tropsch synthesis (FTS is an increasingly important approach for producing liquid fuels and chemicals via syngas—that is, synthesis gas, a mixture of carbon monoxide and hydrogen—generated from coal, natural gas, or biomass. In FTS, dispersed transition metal nanoparticles are used to catalyze the reactions underlying the formation of carbon-carbon bonds. Catalytic activity and selectivity are strongly correlated with the electronic and geometric structure of the nanoparticles, which depend on the particle size, morphology, and crystallographic phase of the nanoparticles. In this article, we review recent works dealing with the aspects of bulk and surface sensitivity of the FTS reaction. Understanding the different catalytic behavior in more detail as a function of these parameters may guide the design of more active, selective, and stable FTS catalysts.

  6. Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst

    Science.gov (United States)

    Li, Wenhui; Wu, Xiaofeng; Li, Shuangde; Tang, Wenxiang; Chen, Yunfa

    2018-04-01

    The synthesis of effective and recyclable Fenton-like catalyst is still a key factor for advanced oxidation processes. Herein, magnetic porous Fe3O4/carbon octahedra were constructed by a two-step controlled calcination of iron-based metal organic framework. The porous octahedra were assembled by interpenetrated Fe3O4 nanoparticles coated with graphitic carbon layer, offering abundant mesoporous channels for the solid-liquid contact. Moreover, the oxygen-containing functional groups on the surface of graphitic carbon endow the catalysts with hydrophilic nature and well-dispersion into water. The porous Fe3O4/carbon octahedra show efficiently heterogeneous Fenton-like reactions for decomposing the organic dye methylene blue (MB) with the help of H2O2, and nearly 100% removal efficiency within 60 min. Furthermore, the magnetic catalyst retains the activity after ten cycles and can be easily separated by external magnetic field, indicating the long-term catalytic durability and recyclability. The good Fenton-like catalytic performance of the as-synthesized Fe3O4/carbon octahedra is ascribed to the unique mesoporous structure derived from MOF-framework, as well as the sacrificial role and stabilizing effect of graphitic carbon layer. This work provides a facile strategy for the controllable synthesis of integrated porous octahedral structure with graphitic carbon layer, and thereby the catalyst holds significant potential for wastewater treatment.

  7. Iron and silicon effect on the phase composition of nickel-beryllium bronzes

    International Nuclear Information System (INIS)

    Zakharov, A.M.; Zakharov, M.V.; Ajvaz'yan, N.G.

    1977-01-01

    In order to specify phase composition and strengthening heat treatment conditions for nickel beryllium bronzes that are promising electrode materials for welding of high strength steels and nickel-base superalloys, the primary section of the quinternary Cu-Ni-Be-Fe-S system was studied at constant nickel and beryllium concentration and varying silicon and iron concentration (max. 4% of every element). The study was made using the metallographic and x-ray phase techniques, determination of alloy solidus temperature, and exessphase microhardness testing. Silicon additions are shown to decrease abruptly and those of iron, in contrast, somewhat to raise the solidus temperature of ternary Cu + 2% Ni + 0.3% Be alloy. When added concurrently, iron compensates for the damaging silicon effect on the solidus temperature of Cu-Ni-Be alloys. The excess phases formed can be used as strengthening agents of Cu-Ni-Be-Si-Fe alloys during quenching and subsequent aging

  8. Experimental analysis of influence of different lubricants types on the multi-phase ironing process

    Directory of Open Access Journals (Sweden)

    Milan Djordjević

    2013-05-01

    Full Text Available This paper is aimed at presenting results of an experimental analysis of the different types of lubricants influence on the multi-phase ironing process. Based on sliding of the metal strip between the two contact elements a special tribological model was adopted. The subject of experimental investigations was variations of the drawing force, contact pressure and the friction coefficient for each type of the applied lubricants. The ironing process was conducted in three-phases at the constant sliding velocity. The objective of this analysis was to compare all the applied lubricants in order to estimate their quality from the point of view of their applicability in the multi-phase ironing process.

  9. EXPERIMENTAL ANALYSIS OF INFLUENCE OF DIFFERENT LUBRICANTS TYPES ON THE MULTI-PHASE IRONING PROCESS

    Directory of Open Access Journals (Sweden)

    Milan Djordjević

    2013-09-01

    Full Text Available This paper is aimed at presenting results of an experimental analysis of the different types of lubricants influence on the multi-phase ironing process. Based on sliding of the metal strip between the two contact elements a special tribological model was adopted. The subject of experimental investigations was variations of the drawing force, contact pressure and the friction coefficient for each type of the applied lubricants. The ironing process was conducted in three-phases at the constant sliding velocity. The objective of this analysis was to compare all the applied lubricants in order to estimate their quality from the point of view of their applicability in the multi-phase ironing process.

  10. Study to determine the content of vanadium, aluminum, nickel, sodium, iron and copper in a catalytic cracking catalyst, by using Atomic Absorption Spectrometry

    International Nuclear Information System (INIS)

    Gomez, J.; Alonso, A.; Tumbarell, O.; Bustanmete, E.

    2003-01-01

    Atomic Absorption Spectrometry (AAS), has the advantage of its simplicity, speed and low cost. All this, together with its high sensibility and selectivity, makes the AAS one the most widely used analytic techniques. The present work shows, the study to determine the content of vanadium, aluminum, nickel, sodium, iron and copper in a catalytic cracking catalyst of a refinery, by using this technique. The results are compared to those of two laboratories which use the ICP-AES and AAS techniques and shows the processing of the statistics with the use of the t of Student and the F of Snedecor. The results using different methods are also shown as well as the recommended application of this results in the chemical characterization of this type of catalysts

  11. Highly selective bimetallic Pt-Cu/Mg(Al)O catalysts for the aqueous-phase reforming of glycerol

    NARCIS (Netherlands)

    Boga, D.A.; Oord, R.; Beale, A.M.; Chung, Y.M.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the

  12. The α-γ-ɛ triple point and phase boundaries of iron under shock compression

    Science.gov (United States)

    Li, Jun; Wu, Qiang; Xue, Tao; Geng, Huayun; Yu, Jidong; Jin, Ke; Li, Jiabo; Tan, Ye; Xi, Feng

    2017-07-01

    The phase transition of iron under shock compression has attracted much attention in recent decades because of its importance in fields such as condensed matter physics, geophysics, and metallurgy. At room temperature, the transition of iron from the α-phase (bcc) to the ɛ-phase (hpc) occurs at a stress of 13 GPa. At high temperature, a triple point followed by transformation to the γ-phase (fcc) is expected. However, the details of the high-temperature phase transitions of iron are still under debate. Here, we investigate the phase-transition behavior of polycrystalline iron under compression from room temperature to 820 K. The results show that the shock-induced phase transition is determined unequivocally from the measured three-wave-structure profiles, which clearly consist of an elastic wave, a plastic wave, and a phase-transition wave. The phase transition is temperature-dependent, with an average rate Δσtr/ΔT of -6.91 MPa/K below 700 K and -34.7 MPa/K at higher temperatures. The shock α-ɛ and α-γ phase boundaries intersect at 10.6 ± 0.53 GPa and 763 K, which agrees with the α-ɛ-γ triple point from early shock wave experiments and recent laser-heated diamond-anvil cell resistivity and in situ X-ray diffraction data but disagrees with the shock pressure-temperature phase diagram reported in 2009 by Zaretsky [J. Appl. Phys. 106, 023510 (2009)].

  13. Iron

    DEFF Research Database (Denmark)

    Hansen, Jakob Bondo; Moen, I W; Mandrup-Poulsen, T

    2014-01-01

    and discuss recent evidence, suggesting that iron is a key pathogenic factor in both type 1 and type 2 diabetes with a focus on inflammatory pathways. Pro-inflammatory cytokine-induced β-cell death is not fully understood, but may include iron-induced ROS formation resulting in dedifferentiation by activation...... of transcription factors, activation of the mitochondrial apoptotic machinery or of other cell death mechanisms. The pro-inflammatory cytokine IL-1β facilitates divalent metal transporter 1 (DMT1)-induced β-cell iron uptake and consequently ROS formation and apoptosis, and we propose that this mechanism provides...

  14. Magnetic properties and phase transformations of iron sulfides synthesized under the hydrothermal method

    Science.gov (United States)

    Li, S. H.; Chen, Y. H.

    2016-12-01

    The iron sulfide nano-minerals possess advantages of high abundance, low cost, and low toxicity. These advantages make them be competitive in the magnetic, electronic, and photoelectric applications. Mackinawite can be used in soil or water remediations. Greigite is very important for paleomagnetic and geochemical environment studies and the anode materials for lithium ion batteries. Besides, greigite is also utilized for hyperthermia and biomedicine. Pyrrhotite can be applied as geothermometry. Due to the above-mentioned reasons, iron sulfide minerals have specific significances and they must be further investigated, like their phase transformations, magnetic properties, and etc. In this study, the iron sulfide minerals were synthesized by using a hydrothermal method. The ex-situ and in-situ X-ray diffraction (XRD) was used to examine the crystal structure and phase transformation of iron sulfide minerals. The Transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) were carried out to investigate their morphology and magnetic properties, respectively. The results suggested that the phase transformation sequence was followed the order: mackinawite → greigite → (smythite) → pyrrhotite. Two pure mineral phases of greigite and pyrrhotite were obtained under the hydrothermal conditions. The morphology of the pure greigite is granular aggregates with a particle size of approximately 30 nm and pyrrhotite presented a hexagonal sheet stacking with a particle size of thousands nanometers. The greigite had a ferri-magnetic behavior and pyrrhotite was weak ferro-magnetic. Both of them had a pseudo-single magnetic domain (PSD) based on the Day's plot from SQUID data. The complete phase-transformation pathways and high magnetization of iron sulfide minerals are observed in this study and these kind of iron sulfide minerals are worthy to further study.

  15. Iron

    Science.gov (United States)

    ... Share: Search the ODS website Submit Search NIH Office of Dietary Supplements Consumer Datos en español Health ... eating a variety of foods, including the following: Lean meat, seafood, and poultry. Iron-fortified breakfast cereals ...

  16. Effects of Iron and Aluminum on Phase Boundaries at 600-800 km Depths

    Science.gov (United States)

    Shim, Sang-Heon; Ye, Yu; Prakapenka, Vitali; Meng, Yue

    2014-05-01

    High-resolution seismic studies have reported complex discontinuity structures at 600-800 km depths. However, the origin of the structures have not been well understood. In order to understand compositional effects, we have measured the post-spinel, post-garnet, and post-ilmenite phase boundaries in MgO-Al2O3-SiO2 (iron free) and CaO-MgO-Al2O3-SiO2-FeO (iron bearing) systems with pyrolitic oxide ratios. In-situ X-ray diffraction measurements were performed at 20-30 GPa and 1500-2300 K in the laser-heated diamond-anvil cell at the GSECARS and HPCAT sectors of the Advanced Photon Source. We use the Pt and Au pressure scales for the iron-free and iron-bearing compositions, respectively. The Pt and Au scales were calibrated with respect to each other in separate experiments. In most experiments, Ar was cryogenically loaded in the sample chamber as a thermal insulation and pressure transmitting medium, except for a few experiments where a KCl medium was used. At temperatures above 1900 K, the post-garnet transition occurs at higher pressures than the post-spinel transition in both the iron-free and iron-bearing systems. At lower temperatures, while the post-ilmenite transition occurs at nearly same pressures as the post-spinel transition in the iron-bearing system, the post-ilmenite transition occurs at slightly higher pressure (1 GPa) than the post-spinel transitions in the iron-free system. In the iron-free system, akimotoite is stable to much higher temperature (2300 K) than previously thought. In the iron-bearing system, the stability of akimotoite is limited to 2050 K. Our data indicate that Al partitions more into akimotoite than garnet in the iron-free system, which is the opposite to what has been found in iron-bearing systems. The high Al content in akimotoite seems to be responsible for the high-temperature stability of akimotoite in the iron-free system. The Clapeyron slope of the post-garnet boundary is greater by a factor of 2.5 in the iron-bearing system

  17. Studies about the transfer phenomena of tritium from liquid to gaseous phase in a catalyst and ordered packing successive system

    International Nuclear Information System (INIS)

    Bornea, Anisia; Cristescu, Ion; Zamfirache, Marius; Varlam, Carmen

    2002-01-01

    The processes for hydrogen isotope separation are very important for nuclear technology. One of the most important processes for tritium separation, is the catalyst isotope exchange water-hydrogen. In a column of isotope exchange tritium is transferred from liquid phase (tritiated heavy water) in gaseous phase (hydrogen). In the experimental setup, which was used, the column of catalytic isotope exchange is filled with successive layers of catalyst and ordered packing. The catalyst consists of 95.5 wt.% of PTFE, 4.1 wt. % of carbon and 0.40 wt. % of platinum and was made of Raschig rings 10 x 10 x 2 mm. The ordered packing was of B7 type and consists of a phosphor bronze wire mesh of 0.18 x 0.48 mm dimension. We analysed the transfer phenomena of tritium from liquid to gaseous phase, in this system. The mathematical model presented in the paper allowed computing experimental data for testing the catalyst performances. In this way the speed constants which characterized the isotopic exchange on the catalysis bed ks, and the distillation on the ordered packing kd, were expressed as function of experimental concentrations and hydrodynamic conditions. (authors)

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO_2 and Al_2O_3. • Interaction between SnO_2 and Al_2O_3 phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn"4"+ cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO_2/Al_2O_3 model catalysts. Our results show that interaction between the Al_2O_3 and SnO_2 phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO_2/Al_2O_3 catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO_2, which probably results from the change of electron concentration on the interface of the SnO_2 and Al_2O_3 phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn"4"+ cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO_2-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  19. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO

    Energy Technology Data Exchange (ETDEWEB)

    Warringham, Robbie; McFarlane, Andrew R.; Lennon, David, E-mail: David.Lennon@Glasgow.ac.uk [School of Chemistry, University of Glasgow, Joseph Black Building, Glasgow, Scotland G12 8QQ (United Kingdom); MacLaren, Donald A. [School of Physics and Astronomy, University of Glasgow, The Kelvin Building, Glasgow, Scotland G12 8QQ (United Kingdom); Webb, Paul B.; Tooze, Robert P. [Sasol Technology UK Ltd., Purdie Building, North Haugh, St Andrews, Fife KY16 9ST (United Kingdom); Taylor, Jon; Ewings, Russell A.; Parker, Stewart F. [ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom)

    2015-11-07

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe{sub 2}O{sub 3}) is distinguished by a relatively intense band at 810 cm{sup −1}, which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered.

  20. The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO

    International Nuclear Information System (INIS)

    Warringham, Robbie; McFarlane, Andrew R.; Lennon, David; MacLaren, Donald A.; Webb, Paul B.; Tooze, Robert P.; Taylor, Jon; Ewings, Russell A.; Parker, Stewart F.

    2015-01-01

    An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe 2 O 3 ) is distinguished by a relatively intense band at 810 cm −1 , which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon feature disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered

  1. 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.

  2. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

    Science.gov (United States)

    Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

    2015-04-28

    Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Phase Diagram for Magnon Condensate in Yttrium Iron Garnet Film

    Science.gov (United States)

    Li, Fuxiang; Saslow, Wayne M.; Pokrovsky, Valery L.

    2013-01-01

    Recently, magnons, which are quasiparticles describing the collective motion of spins, were found to undergo Bose-Einstein condensation (BEC) at room temperature in films of Yttrium Iron Garnet (YIG). Unlike other quasiparticle BEC systems, this system has a spectrum with two degenerate minima, which makes it possible for the system to have two condensates in momentum space. Recent Brillouin Light Scattering studies for a microwave-pumped YIG film of thickness d = 5 μm and field H = 1 kOe find a low-contrast interference pattern at the characteristic wavevector Q of the magnon energy minimum. In this report, we show that this modulation pattern can be quantitatively explained as due to unequal but coherent Bose-Einstein condensation of magnons into the two energy minima. Our theory predicts a transition from a high-contrast symmetric state to a low-contrast non-symmetric state on varying the d and H, and a new type of collective oscillation. PMID:23455849

  4. Effects of Si on microstructure and phase transformation at elevated temperatures in ferritic white cast irons

    Energy Technology Data Exchange (ETDEWEB)

    Wiengmoon, A., E-mail: ampornw@nu.ac.th [Department of Physics, Faculty of Science, Naresuan University, Phitsanulok 65000 (Thailand); Pearce, J.T.H. [Panyapiwat Institute of Management, Nonthaburi 11120 (Thailand); Nusen, S.; Chairuangsri, T. [Department of Industrial Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand)

    2016-10-15

    The effects of Si on microstructure and phase transformation at elevated temperature of ferritic 31wt.%Cr-1.1wt.%C white cast irons with up to 3wt.%Si have been studied. Applications of these irons include parts requiring heat resistance at elevated temperature. The irons were produced by sand casting. The microstructure in as-cast condition and after being subjected to high temperature (700 to 1000 °C) was investigated by light microscopy, X-ray diffraction, and electron microscopy. The results revealed that the as-cast microstructure consisted mainly of primary ferrite dendrites and eutectic (ferrite + M{sub 7}C{sub 3}). Si promotes M{sub 7}C{sub 3}-to-M{sub 23}C{sub 6} transformation in the irons subjected to transformation at elevated temperature, but no sigma phase was found. The extent of M{sub 7}C{sub 3}-to-M{sub 23}C{sub 6} transformation increases proportional to the increasing transformation temperature, holding time and Si content in the irons. For the iron with 1.0wt.%Si content after holding at elevated temperatures, martensite was also found, which could be attributed to carbon accretion effects in eutectic ferrite. Si was incorporated in M{sub 23}C{sub 6} such that M{sub 23}C{sub 6} containing Si can show darker contrast under SEM-BEI as compared to M{sub 7}C{sub 3}; this is the opposite to what has been observed for the cases of typical M{sub 23}C{sub 6} and M{sub 23}C{sub 6} containing Mo or W. The results obtained are important to understand the change in properties of ferritic, high chromium irons containing Si subjected to elevated temperature.

  5. A novel continuous process for synthesis of carbon nanotubes using iron floating catalyst and MgO particles for CVD of methane in a fluidized bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Maghsoodi, Sarah; Khodadadi, Abasali [Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, University of Tehran, Tehran (Iran, Islamic Republic of); Mortazavi, Yadollah, E-mail: mortazav@ut.ac.ir [Nanoelectronics Centre of Excellence, University of Tehran, POB 11365-4563, Tehran (Iran, Islamic Republic of)

    2010-02-15

    A novel continuous process is used for production of carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CVD) of methane on iron floating catalyst in situ deposited on MgO in a fluidized bed reactor. In the hot zone of the reactor, sublimed ferrocene vapors were contacted with MgO powder fluidized by methane feed to produce Fe/MgO catalyst in situ. An annular tube was used to enhance the ferrocene and MgO contacting efficiency. Multi-wall as well as single-wall CNTs was grown on the Fe/MgO catalyst while falling down the reactor. The CNTs were continuously collected at the bottom of the reactor, only when MgO powder was used. The annular tube enhanced the contacting efficiency and improved both the quality and quantity of CNTs. The SEM and TEM micrographs of the products reveal that the CNTs are mostly entangled bundles with diameters of about 10-20 nm. Raman spectra show that the CNTs have low amount of amorphous/defected carbon with I{sub G}/I{sub D} ratios as high as 10.2 for synthesis at 900 deg. C. The RBM Raman peaks indicate formation of single-walled carbon nanotubes (SWNTs) of 1.0-1.2 nm diameter.

  6. Oxidative Debromination and Degradation of Tetrabromo-bisphenol A by a Functionalized Silica-Supported Iron(III-tetrakis(p-sulfonatophenylporphyrin Catalyst

    Directory of Open Access Journals (Sweden)

    Masami Fukushima

    2013-05-01

    Full Text Available Tetrabromobisphenol A (TBBPA, a commonly used brominated flame retardant, also functions as an endocrine disruptor. Thus, the degradation of TBBPA has attracted considerable interest among the scientific community. Iron(III-porphyrin complexes are generally regarded as “green” catalysts and have been reported to catalyze the efficient degradation and dehalogenation of halogenated phenols in environmental wastewaters. However, they are quickly deactivated due to self-degradation in the presence of an oxygen donor, such as KHSO5. In the present study, an iron(III-tetrakis (p-sulfonatophenyl-porphyrin (FeTPPS was immobilized on imidazole-modified silica (FeTPPS/IPS via coordination of the Fe(III with the nitrogen atom in imidazole to suppress self-degradation and thus enhance the catalyst reusability. The oxidative degradation and debromination of TBBPA and the influence of humic acid (HA, a major component in leachates, on the oxidation of TBBPA was investigated. More than 95% of the TBBPA was degraded in the pH range from 3 to 8 in the absence of HA, while the optimal pH for the reaction was at pH 8 in the presence of HA. Although the rate of degradation was decreased in the presence of HA, over 95% of the TBBPA was degraded within 12 h in the presence of 28 mg-C L−1 of HA. At pH 8, the FeTPPS/IPS catalyst could be reused up to 10 times without any detectable loss of activity for TBBPA for degradation and debromination, even in the presence of HA.

  7. Solid-phase extraction (SPE) of Iron using Lanthanum Silicate ion exchange

    International Nuclear Information System (INIS)

    Kiarostami, V.; Husain, W.

    2002-01-01

    Solid-phase extraction (SPE) is gaining wide use as an effective and speedy technique which reduces solvent usage, disposal costs and extraction time. The analyte is adsorbed from solution onto a solid adsorbent, which is followed by elution of the analyte with a solvent appropriate for instrumental analysis. However, there is an increasing need for new selective adsorbents to expand the area of this technique. Lanthanum silicate ion exchanger, which shows unusual selectivity elements and in this study, it was employed to develop a SPE method for iron ion. Special experiments such as determination of distribution coefficient for iron ion in different solvent systems have been determined

  8. Formation of gas-phase π-allyl radicals from propylene over bismuth oxide and γ-bismuth molybdate catalysts

    International Nuclear Information System (INIS)

    Martir, W.; Lunsford, J.H.

    1981-01-01

    Gas-phase π-allyl radicals were produced when propylene reacted over Bi 2 O 3 and γ-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10 -3 and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than γ-bismuth molybdate. By contrast α-bismuth molybdate was ineffective in forming allyl radicals and MoO 3 acted as a sink for radicals which were produced elsewhere in the system. Comparison of the π-allyl radical and the stable product concentrations over Bi 2 O 3 revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system

  9. Determination of Iron Species by Combination of Solvent Assisted-Dispersive Solid Phase Extraction and Spectrophotometry

    Directory of Open Access Journals (Sweden)

    Zahra Dehghani

    2015-06-01

    Full Text Available A simple, rapid and sensitive solvent assisted-dispersive solid phase extraction method was developed for the extraction of iron(II prior to its spectrophotometric determination. The Fe(II reacted with 2,4,6-tris(2-pyridyl-1,3,5-triazine, neutralized with sodium dodecyl sulfate and extracted onto the fine particles of benzophenone which were formed upon rapid injection of a mixture of benzophenone as the sorbent and ethanol as the disperser solvent into the aqueous solution. After phase separation, the sedimented phase containing the complex was dissolved in ethanol and the analyte concentration was determined by measuring its absorption at 594 nm. Total iron was determined after the reduction of Fe(III to Fe(II with hydroxylamine hydrochloride. Under the optimized conditions, an enhancement factor of 32, the detection limit of 0.16 µg l-1, and the relative standard deviation of 1.9% (n = 6 at 20 µg l-1 concentration level of Fe(II were achieved. The method was successfully applied to the determination of iron species in water samples and total iron in infant dry formula milk, apple, rice, spinach and parsley samples.

  10. The mechanism of stereospecific C-H oxidation by Fe(Pytacn) complexes: bioinspired non-heme iron catalysts containing cis-labile exchangeable sites.

    Science.gov (United States)

    Prat, Irene; Company, Anna; Postils, Verònica; Ribas, Xavi; Que, Lawrence; Luis, Josep M; Costas, Miquel

    2013-05-17

    A detailed mechanistic study of the hydroxylation of alkane C-H bonds using H2O2 by a family of mononuclear non heme iron catalysts with the formula [Fe(II)(CF3SO3)2(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis-labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C-H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C-H hydroxylation is performed by highly electrophilic [Fe(V)(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C-H bond, followed by rebound of the hydroxyl ligand. The [Fe(V)(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic-labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. NATURAL IRON OXIDE AS A HETEROGENEOUS PHOTO-FENTON-LIKE CATALYST FOR THE DEGRADATION OF 1-NAPHTHOL UNDER ARTIFICIAL AND SOLAR LIGHT

    Directory of Open Access Journals (Sweden)

    L MAMMERI

    2014-07-01

    Full Text Available A heterogeneous photo-Fenton-like degradation process of 1-naphthol (1-NP promoted by natural iron oxide (NIO in the presence of H2O2 was studied under artificial (365 nm and solar irradiation. This is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural waters. Furthermore, iron oxides function as catalysts in chemical oxidation processes used with H2O2 for treatment of contaminated waters. The NIO used in this study was characterized by X-ray diffraction (XRD, X-ray fluorescence and Brunauer–Emmett–Teller (BET methods. The results show that the NIO is a composite material that contains predominantly crystalline hematite particales (Fe2O3. The Fe2O3 in NIO was able to initiate the Fenton-like and photo-Fenton-like reactions. The effects of initial pH, catalyst dosage, H2O2 concentration and the wavelength of the light source (UV and solar on the photodegradation of 1-NP were investigated. The optimal content of the NIO was 1 g L-1 and the optimal H2O2 concentration was 10 mM. The degradation could occur efficiently over a wide pH range of 3-8.3. Furthermore, an important effect of light was observed. The photo-oxidation of 1-NP in NIO-H2O2 system under solar light was significantly accelerated in comparison with artificial irradiation at 365 nm.

  12. Synergy effects between bismuth molybdate catalyst phases (Bi/Mo from 0.57 to 2) for the selective oxidation of propylene to arcrolein

    DEFF Research Database (Denmark)

    Le, Minh Thang; Well, Willy van; Stoltze, Per

    2005-01-01

    In this work, the synergy effect between different phases of bismuth molybdate catalysts was investigated systematically. The catalysts were prepared by spray drying and had a Bi/Mo atomic between 0.57 and 2. It is found that the synergy effect is only observed in mixtures containing γ-phase. A m......-phase. A mixture with Bi/Mo ratio = 1.3 consisting of γ- and α-phase, exhibits the highest activity. Less homogeneous ‘artificial mixtures’ exhibit reduced synergy effects when compared to homogeneous ‘in situ mixtures’.......In this work, the synergy effect between different phases of bismuth molybdate catalysts was investigated systematically. The catalysts were prepared by spray drying and had a Bi/Mo atomic between 0.57 and 2. It is found that the synergy effect is only observed in mixtures containing γ...

  13. Resource Recovery and Reuse: Recycled Magnetically Separable Iron-based Catalysts for Phosphate Recovery and Arsenic Removal

    Science.gov (United States)

    Environmentally friendly processes that aid human and environmental health include recovering, recycling, and reusing limited natural resources and waste materials. In this study, we re-used Iron-rich solid waste materials from water treatment plants to synthesize magnetic iron-o...

  14. Quantum molecular dynamics of warm dense iron and a five-phase equation of state

    Science.gov (United States)

    Sjostrom, Travis; Crockett, Scott

    2018-05-01

    Through quantum molecular dynamics (QMD), utilizing both Kohn-Sham (orbital-based) and orbital-free density functional theory, we calculate the equation of state of warm dense iron in the density range 7 -30 g/cm 3 and temperatures from 1 to 100 eV. A critical examination of the iron pseudopotential is made, from which we find a significant improvement at high pressure to the previous QMD calculations of Wang et al. [Phys. Rev. E 89, 023101 (2014), 10.1103/PhysRevE.89.023101]. Our results also significantly extend the ranges of density and temperature that were attempted in that prior work. We calculate the shock Hugoniot and find very good agreement with experimental results to pressures over 20 TPa. These results are then incorporated with previous studies to generate a five-phase equation of state for iron.

  15. Nanographene synthesized in triple-phase plasmas as a highly durable support of catalysts for polymer electrolyte fuel cells

    Science.gov (United States)

    Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

    2018-04-01

    Nanographene was synthesized in triple-phase plasmas comprising a gaseous phase, a gas-liquid boundary layer, and an in-liquid phase using a setup in which one electrode was placed in the gaseous phase while the other was immersed in the liquid phase. The triple-phase plasmas were generated using a pure alcohol, such as ethanol, 1-propanol, or 1-butanol, by applying a high voltage to a pair of electrodes made of copper or graphite. The nanographene synthesized using ethanol had high durability and thus could serve as a catalyst support in polymer electrolyte fuel cells (PEFCs). The PEFCs exhibited low degradation rates in the high-potential cycle test of a half-cell, as a result of which, a loss of only 10% was observed in the effective electrochemical surface area of Pt, even after 10,000 cycles.

  16. Methods of making textured catalysts

    Science.gov (United States)

    Werpy, Todd [West Richland, WA; Frye, Jr., John G.; Wang, Yong [Richland, WA; Zacher, Alan H [Kennewick, WA

    2010-08-17

    A textured catalyst having a hydrothermally-stable support, a metal oxide and a catalyst component is described. Methods of conducting aqueous phase reactions that are catalyzed by a textured catalyst are also described. The invention also provides methods of making textured catalysts and methods of making chemical products using a textured catalyst.

  17. Fischer-Tropsch synthesis in slurry-phase reactors using Co/SBA-15 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, J.J.; Lima, L.A.; Lima, W.S.; Rodrigues, M.G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], e-mail: meiry@deq.ufcg.edu.br; Fernandes, F.A.N. [Universidade Federal do Ceara (UFCE), CE (Brazil). Dept. de Engenharia Quimica

    2011-07-15

    The objective of this work is to describe the production of bifunctional catalysts using the incipient humidity method, producing catalysts with 15 wt.% cobalt supported in SBA-15 molecular sieve, to be applied in the Fischer-Tropsch (FT) reaction. The originality of this work is its focus on the use of a 15 wt.% Co/SBA-15 catalyst in FT synthesis in slurry reactors. The deposition of cobalt over SBA-15 support was accomplished by impregnation with a 0.1-M aqueous solution of cobalt nitrate. The Fischer-Tropsch synthesis was carried out with the catalyst at 240 deg C and 20 atm, under a COH{sub 2} atmosphere (molar ratio= 1), in a slurry reactor for 8 hours. X-ray diffraction measurements showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co{sub 3}O{sub 4} in the catalyst. The addition of cobalt in the SBA-15 decreased the specific superficial area of the molecular sieve. The 15 wt.% Co/SBA-15 catalyst had a 40% CO conversion rate and a high selectivity towards the production of C{sub 5}{sup +} (53.9% after 8 hours). (author)

  18. Thin film phase diagram of iron nitrides grown by molecular beam epitaxy

    Science.gov (United States)

    Gölden, D.; Hildebrandt, E.; Alff, L.

    2017-01-01

    A low-temperature thin film phase diagram of the iron nitride system is established for the case of thin films grown by molecular beam epitaxy and nitrided by a nitrogen radical source. A fine-tuning of the nitridation conditions allows for growth of α ‧ -Fe8Nx with increasing c / a -ratio and magnetic anisotropy with increasing x until almost phase pure α ‧ -Fe8N1 thin films are obtained. A further increase of nitrogen content below the phase decomposition temperature of α ‧ -Fe8N (180 °C) leads to a mixture of several phases that is also affected by the choice of substrate material and symmetry. At higher temperatures (350 °C), phase pure γ ‧ -Fe4N is the most stable phase.

  19. Poly(Ionic Liquid: A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

    Directory of Open Access Journals (Sweden)

    Lan Yao

    2018-03-01

    Full Text Available Poly(ionic liquids (PILs have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC system for Cu-based atom transfer radical polymerization (ATRP was constructed. The copper catalyst (CuBr2 used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

  20. Characterisation of iron inclusion during the formation of calcium sulfoaluminate phase

    International Nuclear Information System (INIS)

    Idrissi, M.; Diouri, A.; Damidot, D.; Greneche, J.M.; Talbi, M. Alami; Taibi, M.

    2010-01-01

    The iron distribution among the sulfoaluminate clinker phases and its ability to enter the calcium sulfoaluminate lattice in solid solution can have a significant influence on manufacturing process and reactivity of calcium sulfoaluminate (CSA) cements. X-ray diffraction (XRD) analysis, Moessbauer spectroscopy, scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analysis system (EDAX) and infrared spectroscopy were used to identify the mineralogical conditions of iron inclusion during the formation of calcium sulfoaluminate (C 4 A 3 S) phase from different mixtures in the CaO-Al 2 O 3 -Fe 2 O 3 -SO 3 system. The mixtures, heated in a laboratory electric oven, contained stoichiometric amounts of reagent grade CaCO 3 , Al 2 O 3 , Fe 2 O 3 and CaSO 4 .2H 2 O for the synthesis of Ca 4 Al (6- 2x) Fe 2x SO 16 , where x, comprised between 0 and 3, is the mole number of Al 2 O 3 substituted by Fe 2 O 3 . With x increasing from 0 to 1.5, both the iron content of C 4 A 3 S phase and the amounts of side components such as C 2 F and CS increased. For x values included in the range of 1.5-3.0, at temperatures higher than 1200 o C, melting phenomena were observed and, instead of the C 4 A 3 S solid solution, ferritic phases and anhydrite were formed.

  1. Characterization of catalysts by Moessbauer spectroscopy: An application to the study of Fischer-Tropsch, hydrotreating and super Claus catalysts

    International Nuclear Information System (INIS)

    Kraan, A.M. van der; Boellaard, E.; Craje, M.W.J.

    1993-01-01

    Moessbauer spectroscopy is an excellent in-situ technique for the identification of phases present in catalysts. Applied to metallic iron catalysts used in the Fischer-Tropsch reaction it reveals a detailed picture of the carburization process and provides insight into the relation between the properties of the catalytic material and its activity. The influence of a support and the effect of alloying iron with an (in)active metal on the catalytic performance is discussed for Fe, Cu-Fe and Ni-Fe systems. In addition, Moessbauer spectroscopy is used for the identification of 'Co-sulfide' species present in sulfided Co and CoMo catalysts applied in one of the largest chemical processes in the world, the hydrotreatment of crude oil. A structural model is proposed. Finally, the contribution of Moessbauer spectroscopic studies to the development of a new catalyst for cleaning of Claus tail gas via selective oxidation of hydrogen sulfide to elemental sulfur is discussed. (orig.)

  2. Effect of Al content on the gas-phase dehydration of glycerol over silica-alumina-supported silicotungstic acid catalysts

    International Nuclear Information System (INIS)

    Kim, Yong Tae; You, Su Jin; Park, Eun Duck; Jung, Kwangdeog

    2012-01-01

    The gas-phase dehydration of glycerol to acrolein was carried out over silicotungstic acid (H 4 SiW 12 O 40 ·xH 2 O, HSiW) catalysts supported on SiO 2 , η-Al 2 O 3 , and silica-alumina with different Al contents. The HSiW catalysts supported on silica-alumina showed higher glycerol conversions and acrolein yields during the initial 2 h at 315.deg.C than did SiO 2 - and η-Al 2 O 3 -supported HSiW catalysts. Among the tested catalysts, HSiW/Si 0.9 Al 0.1Ox exhibited the highest space-time yield during the initial 2 h. The loaded HSiW species can change the acid types and suppress the formation of carbonaceous species on Al-rich silica-alumina. The deactivated HSiW supported on silica-alumina can be fully regenerated after calcination in air at 500.deg.C. As long as the molar ratio between water and glycerol was in the range of 2-11, the acrolein selectivity increased significantly with increasing water content in the feed, while the surface carbon content decreased owing to the suppression of heavy compounds

  3. Metal catalysts fight back

    OpenAIRE

    George Marsh

    1998-01-01

    In recent years organometallic catalysts, especially metallocenes, have been a major focus of attention in terms of polymerisation chemistry. But the news earlier this year of a family of iron-based catalysts able to rival the effectiveness of both conventional and metallocene catalysts in the polymerisation of ethylene has excited the plastics industry. Because of the impact of this discovery and its potential as a route to lower-priced commodity plastics in the future, it may be useful at t...

  4. Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts.

    Science.gov (United States)

    Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G

    2015-06-22

    The catalytic performance of homogeneous Lewis acid catalysts and their interaction with Ru/C catalyst are studied in the catalytic transfer hydrogenation of furfural by using 2-propanol as a solvent and hydrogen donor. We find that Lewis acid catalysts hydrogenate the furfural to furfuryl alcohol, which is then etherified with 2-propanol. The catalytic activity is correlated with an empirical scale of Lewis acid strength and exhibits a volcano behavior. Lanthanides are the most active, with DyCl3 giving complete furfural conversion and a 97 % yield of furfuryl alcohol at 180 °C after 3 h. The combination of Lewis acid and Ru/C catalysts results in synergy for the stronger Lewis acid catalysts, with a significant increase in the furfural conversion and methyl furan yield. Optimum results are obtained by using Ru/C combined with VCl3 , AlCl3 , SnCl4 , YbCl3 , and RuCl3 . Our results indicate that the combination of Lewis acid/metal catalysts is a general strategy for performing tandem reactions in the upgrade of furans. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Effect of Chlorine precursor in surface and cataytic properties of Fe/TiO2 Catalysts

    OpenAIRE

    López, Tessi; Pecchi, Gina; Moreno, Abel; García Fierro, José Luis; Gómez, R.; Reyes, P.

    2002-01-01

    Titania-supported iron (1wt%) catalysts were prepared by the sol-gel method using different gelation pH (3 and 9), metal precursors (FeCl2 and FeCl3) and calcination temperatures (873 and 1073K). Characterization data of calcined catalysts revealed that in all samples the dominant iron species is Fe3+ and the crystalline phase of the TiO2 substrate depends on the gelation pH and the metal precursor used. It was found that in the Fe/TiO2 ex-FeCl3 samples an important part of the iron ions beca...

  6. Dynamic strength properties and alpha-phase shock Hugoniot of iron and steel

    Science.gov (United States)

    Thomas, S. A.; Hawkins, M. C.; Matthes, M. K.; Gray, G. T.; Hixson, R. S.

    2018-05-01

    The properties of iron and steel are of considerable interest scientifically to the dynamic materials properties' community, as well as to a broader audience, for many applications. This is true in part because of the existence of a solid-solid phase (α-ɛ) transition at relatively modest stress (13 GPa). Because of this, there is a significant amount of data on iron and steel alloy shock compression properties at stresses above 13 GPa, but much less fundamental data under stress conditions lower than that, where the metals are in the α-phase. New data have been obtained under relatively low stress (below 10 GPa) conditions in which samples are subjected to low-velocity symmetric impact on the order of 0.2 to 0.4 km/s. We used well-developed flyer plate impact methods combined with velocity interferometry to measure wave speeds and strength properties in compression and tension. The shock α-phase Hugoniot data reported here are compared with literature values. A comparison of spall strength and Hugoniot elastic limit is made between different types of steel studied and for pure iron.

  7. Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

    Science.gov (United States)

    Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

    2013-04-29

    MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

  8. Effect of Iron Impurity on the Phase Composition, Structure and Properties of Magnesium Alloys Containing Manganese and Aluminum

    Science.gov (United States)

    Volkova, E. F.

    2017-07-01

    Results of a study of the interaction between iron impurity and manganese and aluminum alloying elements during formation of phase composition in alloys of the Mg - Mn, Mg - Al, Mg - Al - Mn, and Mg - Al - Zn - Mn systems are presented. It is proved that this interaction results in introduction of Fe into the intermetallic phase. The phase compositions of model magnesium alloys and commercial alloys MA2-1 and MA5 are studied. It is shown that both manganese and aluminum may bind the iron impurity into phases. Composite Fe-containing intermetallic phases of different compositions influence differently the corrosion resistance of magnesium alloys.

  9. Interstitial-phase precipitation in iron-base alloys: a comparative study

    International Nuclear Information System (INIS)

    Pelton, A.R.

    1982-06-01

    Recent developments have elucidated the atomistic mechanisms of precipitation of interstitial elements in simple alloy systems. However, in the more technologically important iron base alloys, interstitial phase precipitation is generally not well understood. The present experimental study was therefore designed to test the applicability of these concepts to more complex ferrous alloys. Hence, a comparative study was made of interstitial phase precipitation in ferritic Fe-Si-C and in austenitic phosphorus-containing Fe-Cr-Ni steels. These systems were subjected to a variety of quench-age thermal treatments, and the microstructural development was subsequently characterized by transmission electron microscopy

  10. Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

    Science.gov (United States)

    Nguyen, Luan; Tao, Franklin Feng

    2018-02-01

    Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

  11. Formation of Multiple-Phase Catalysts for the Hydrogen Storage of Mg Nanoparticles by Adding Flowerlike NiS.

    Science.gov (United States)

    Xie, Xiubo; Ma, Xiujuan; Liu, Peng; Shang, Jiaxiang; Li, Xingguo; Liu, Tong

    2017-02-22

    In order to enhance the hydrogen storage properties of Mg, flowerlike NiS particles have been successfully prepared by solvothermal reaction method, and are subsequently ball milled with Mg nanoparticles (NPs) to fabricate Mg-5 wt % NiS nanocomposite. The nanocomposite displays Mg/NiS core/shell structure. The NiS shell decomposes into Ni, MgS and Mg 2 Ni multiple-phases, decorating on the surface of the Mg NPs after the first hydrogen absorption and desorption cycle at 673 K. The Mg-MgS-Mg 2 Ni-Ni nanocomposite shows enhanced hydrogenation and dehydrogenation rates: it can quickly uptake 3.5 wt % H 2 within 10 min at 423 K and release 3.1 wt % H 2 within 10 min at 573 K. The apparent hydrogen absorption and desorption activation energies are decreased to 45.45 and 64.71 kJ mol -1 . The enhanced sorption kinetics of the nanocomposite is attributed to the synergistic catalytic effects of the in situ formed MgS, Ni and Mg 2 Ni multiple-phase catalysts during the hydrogenation/dehydrogenation process, the porthole effects for the volume expansion and microstrain of the phase transformation of Mg 2 Ni and Mg 2 NiH 4 and the reduced hydrogen diffusion distance caused by nanosized Mg. This novel method of in situ producing multiple-phase catalysts gives a new horizon for designing high performance hydrogen storage material.

  12. Influence of phase composition and structure of V-Mo mixed catalysts on the activity and selectivity in the oxidation of benzene to maleic anhydride

    International Nuclear Information System (INIS)

    Kripylo, P.; Ritter, D.; Hahn, H.; Spiess, H.; Kraak, P.

    1981-01-01

    Whereas MoO 3 and phosphate stabilize the low valence states of vanadium in the phase structure of V-Mo mixed catalysts, CoO influences the activity only, but not the selectivity. The catalysts show maxima of activity and selectivity at V/Mo ratios of 4 to 6. Ageing is caused by phase separation connected with the appearance of an MoO 3 phase and an increase of the V/Mo ratio in the phase of the active component

  13. Dispersed catalysts for transforming extra heavy crude oil into transportable upgraded crude: phase identification

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, S.; Canizales, E.; Machin, I. [Gerencia Depttal de Investigacion Estrategica en Refinacion PDVSA Intevep (Venezuela); Segovia, X.; Rivas, A.; Lopez, E.; Pena, J.P.; Rojas, J.D.; Sardella, R. [Gerencia Depttal de Infraestructura y Mejoramiento en Faja Petrolifera PDVSA Intevep (Venezuela)

    2011-07-01

    A new technology to convert extra heavy crude oil into transportable upgraded crude has been developed. A water/oil emulsion composed of steam and catalyst precursors is introduced in the feed which then generates unsupported dispersed catalyst in situ under thermal decomposition. The aim of this paper is to characterize the particles. The study was conducted in a laboratory and on a pilot scale on three different vacuum residues using high resolution transmission electron microscopy and a transmission electron microscope. Results showed that the particles were formed by oxides and inorganic sulphur based in transition metals and their sizes ranged between 5 and 120 nm; in addition, good dispersion was observed. This study demonstrated that the process involved in the generation of dispersed catalyst is extremely complex and showed that further work with heavy crude oils and its residua is required to understand the mechanisms involved.

  14. Iron Damage and Spalling Behavior below and above Shock Induced α ε Phase Transition

    International Nuclear Information System (INIS)

    Voltz, Christophe; Buy, Francois; Roy, Gilles

    2006-01-01

    The study of dynamic damage and fracture of iron has been undertaken below and above phase transition by series of time resolved experiments using both light gas launcher and powder gun. Shock wave tests were conducted by symmetrical impacts of high purity iron. To reveal the material behavior we have done shock experiments where the target is covered with a window in order to limit release amplitude and to avoid specimen fragmentation. Metallurgical analysis of soft recovered samples yields information about damage and fracture processes related to thermo-mechanical loading paths. Tests conducted without window allow studying effects of both phase change and release transition. Optical and SEM characterizations lead us to observe several modes of damage: brittle, ductile diffuse with void growth and heavily localized smooth one. These figures are related with: rarefaction shock waves or interfaces between transformed and not transformed iron. Simulations are performed with the 1D to compare experimental data with numerical results. We explain post-mortem observations by the complex shock wave structure interactions: P1 and P2 shock fronts associated with some corresponding shock release during unloading stages

  15. Photodegradation of polycyclic aromatic hydrocarbon pyrene by iron oxide in solid phase

    International Nuclear Information System (INIS)

    Wang, Y.; Liu, C.S.; Li, F.B.; Liu, C.P.; Liang, J.B.

    2009-01-01

    To better understand the photodegradation of polycyclic aromatic hydrocarbons (PAH) in solid phase in natural environment, laboratory experiments were conducted to study the influencing factors, kinetics and intermediate compound of pyrene photodegradation by iron oxides. The results showed that the pyrene photodegradation rate followed the order of α-FeOOH > α-Fe 2 O 3 > γ-Fe 2 O 3 > γ-FeOOH at the same reaction conditions. Lower dosage of α-FeOOH and higher light intensity increased the photodegradation rate of pyrene. Iron oxides and oxalic acid can set up a photo-Fenton-like system without additional H 2 O 2 in solid phase to enhance the photodegradation of pyrene under UV irradiation. All reaction followed the first-order reaction kinetics. The half-life (t 1/2 ) of pyrene in the system showed the higher efficiencies of using iron oxide as photocatalyst to degrade pyrene. Intermediate compound pyreno was found during photodegradation reactions by gas chromatography-mass spectrometry (GC-MS). The photodegradation efficiency for PAHs in this photo-Fenton-like system was also confirmed by using the contaminated soil samples. This work provides some useful information to understand the remediation of PAHs contaminated soils by photochemical techniques under practical condition

  16. Iron Intermetallic Phases in the Alloy Based on Al-Si-Mg by Applying Manganese

    Directory of Open Access Journals (Sweden)

    Podprocká R.

    2017-09-01

    Full Text Available Manganese is an effective element used for the modification of needle intermetallic phases in Al-Si alloy. These particles seriously degrade mechanical characteristics of the alloy and promote the formation of porosity. By adding manganese the particles are being excluded in more compact shape of “Chinese script” or skeletal form, which are less initiative to cracks as Al5FeSi phase. In the present article, AlSi7Mg0.3 aluminium foundry alloy with several manganese content were studied. The alloy was controlled pollution for achieve higher iron content (about 0.7 wt. % Fe. The manganese were added in amount of 0.2 wt. %, 0.6 wt. %, 1.0 wt. % and 1.4 wt. %. The influence of the alloying element on the process of crystallization of intermetallic phases were compared to microstructural observations. The results indicate that increasing manganese content (> 0.2 wt. % Mn lead to increase the temperature of solidification iron rich phase (TAl5FeSi and reduction this particles. The temperature of nucleation Al-Si eutectic increase with higher manganese content also. At adding 1.4 wt. % Mn grain refinement and skeleton particles were observed.

  17. COMPUTER MODELING OF STRAINS ON PHASE BOUNDARIES IN DUCTILE CAST IRON AT HOT EXTRUSION

    Directory of Open Access Journals (Sweden)

    A. I. Pokrovsky

    2017-01-01

    Full Text Available The computer modeling of the strain distribution in the structure of ductile iron with ferrite-pearlite matrix and inclusions of spherical graphite dependence on increasing degree of deformation during direct hot extrusion was researched. Using a software system of finite-element analysis ANSYS the numerical values of the strains at the phase boundaries: ferrite-perlite, graphiteferrite and also inside the graphite inclusions were defined. The analysis of the strain distribution in the investigated structures was performed and local zones of increased strains were discovered. The results of modeling are compared with metallographic analysis and fracture patterns. The obtained results could be used in the prediction of fracture zones in the cast iron products. 

  18. Co-processing of lignite-plastic mixtures into liquid distillate fractions in the presence of iron catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, B.N.; Sharypov, V.I.; Beregovtsova, N.G.; Baryshnikov, S.V.; Doroginskaya, A.N. [Russian Academy of Sciences, Krasnoyarsk (Russian Federation). Inst. of Chemistry of Natural Organic Materials Sibirian Branch

    1997-12-31

    Some features of co-processing of Kansk-Achinsk lignite with plastics into hydrocarbon mixtures in the presence of activated iron-containing minerals (hematite, magnetite, pyrrhotite) were investigated under various operating parameters. The following catalytic processes were studied: pyrolysis in an inert atmosphere, hydropyrolysis and water-steam cracking. (orig.)

  19. Template-assisted hydrothermally synthesized iron-titanium binary oxides and their application as catalysts for ethyl acetate oxidation

    Czech Academy of Sciences Publication Activity Database

    Tsoncheva, T.; Ivanova, R.; Dimitrov, M.; Paneva, D.; Kovacheva, D.; Henych, Jiří; Vomáčka, Petr; Kormunda, M.; Velinov, N.; Mitov, I.; Štengl, Václav

    2016-01-01

    Roč. 528, NOV (2016), s. 24-35 ISSN 0926-860X R&D Projects: GA MŠk(CZ) LM2015073 Institutional support: RVO:61388980 Keywords : Effect of Fe/Ti ratio and temperature of hydrothermal treatment * Hydrothermal synthesis * Iron-titanium binary oxides Subject RIV: CA - Inorganic Chemistry Impact factor: 4.339, year: 2016

  20. The role of equilibrium volume and magnetism on the stability of iron phases at high pressures.

    Science.gov (United States)

    Alnemrat, S; Hooper, J P; Vasiliev, I; Kiefer, B

    2014-01-29

    The present study provides new insights into the pressure dependence of magnetism by tracking the hybridization between crystal orbitals for pressures up to 600 GPa in the known hcp, bcc and fcc iron. The Birch-Murnaghan equation of state parameters are; bcc: V0 = 11.759 A(3)/atom, K0 = 177.72 GPa; hcp: V0 = 10.525 A(3)/atom, K0 = 295.16 GPa; and fcc: V0 = 10.682 A(3)/atom, K0 = 274.57 GPa. These parameters compare favorably with previous studies. Consistent with previous studies we find that the close-packed hcp and fcc phases are non-magnetic at pressures above 50 GPa and 60 GPa, respectively. The principal features of magnetism in iron are predicted to be invariant, at least up to ∼6% overextension of the equilibrium volume. Our results predict that magnetism for overextended fcc iron disappears via an intermediate spin state. This feature suggests that overextended lattices can be used to stabilize particular magnetic states. The analysis of the orbital hybridization shows that the magnetic bcc structure at high pressures is stabilized by splitting the majority and minority spin bands. The bcc phase is found to be magnetic at least up to 600 GPa; however, magnetism is insufficient to stabilize the bcc phase itself, at least at low temperatures. Finally, the analysis of the orbital contributions to the total energy provides evidence that non-magnetic hcp and fcc phases are likely more stable than bcc at core earth pressures.

  1. 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.

  2. Aqueous phase reforming of ethylene glycol - Role of intermediates in catalyst performance

    NARCIS (Netherlands)

    de Vlieger, Dennis; Mojet, Barbara; Lefferts, Leonardus; Seshan, Kulathuiyer

    2012-01-01

    Liquid product formation during the aqueous catalytic reforming of ethylene glycol (EG) was studied up to 450 °C and 250 bar pressure. Methanol, ethanol, and acetic acid were the main liquid by-products during EG reforming in the presence of alumina-supported Pt and Pt–Ni catalysts. The effect of

  3. Liquid phase in situ hydrodeoxygenation of biomass-derived phenolic compounds to hydrocarbons over bifunctional catalysts

    Science.gov (United States)

    Junfeng Feng; Chung-yun Hse; Zhongzhi Yang; Kui Wang; Jianchun Jiang; Junming Xu

    2017-01-01

    The objective of this study was to find an effective method for converting renewable biomass-derived phenolic compounds into hydrocarbons bio-fuel via in situ catalytic hydrodeoxygenation. The in situ hydrodeoxygenation of biomass-derived phenolic compounds was carried out in methanol-water solvent over bifunctional catalysts of Raney Ni and HZSM-5 or H-Beta. In the in...

  4. Microbial Reducibility of Fe(III Phases Associated with the Genesis of Iron Ore Caves in the Iron Quadrangle, Minas Gerais, Brazil

    Directory of Open Access Journals (Sweden)

    Ceth W. Parker

    2013-11-01

    Full Text Available The iron mining regions of Brazil contain thousands of “iron ore caves” (IOCs that form within Fe(III-rich deposits. The mechanisms by which these IOCs form remain unclear, but the reductive dissolution of Fe(III (hydroxides by Fe(III reducing bacteria (FeRB could provide a microbiological mechanism for their formation. We evaluated the susceptibility of Fe(III deposits associated with these caves to reduction by the FeRB Shewanella oneidensis MR-1 to test this hypothesis. Canga, an Fe(III-rich duricrust, contained poorly crystalline Fe(III phases that were more susceptible to reduction than the Fe(III (predominantly hematite associated with banded iron formation (BIF, iron ore, and mine spoil. In all cases, the addition of a humic acid analogue enhanced Fe(III reduction, presumably by shuttling electrons from S. oneidensis to Fe(III phases. The particle size and quartz-Si content of the solids appeared to exert control on the rate and extent of Fe(III reduction by S. oneidensis, with more bioreduction of Fe(III associated with solid phases containing more quartz. Our results provide evidence that IOCs may be formed by the activities of Fe(III reducing bacteria (FeRB, and the rate of this formation is dependent on the physicochemical and mineralogical characteristics of the Fe(III phases of the surrounding rock.

  5. Diesel Emission Control- Sulfur Effects (DECSE) Program- Phase II Summary Report: NOx Adsorber Catalysts; FINAL

    International Nuclear Information System (INIS)

    None

    2000-01-01

    The investigations performed in this project demonstrated the ability to develop a NO(sub x) regeneration strategy including both an improved lean/rich modulation cycle and rich engine calibration, which resulted in a high NO(sub x) conversion efficiency over a range of operating temperatures. A high-temperature cycle was developed to desulfurize the NO(sub x) absorber catalyst. The effectiveness of the desulfurization process was demonstrated on catalysts aged using two different sulfur level fuels. The major findings of this project are as follows: (1) The improved lean/rich engine calibration achieved as a part of this test project resulted in NO(sub x) conversion efficiencies exceeding 90% over a catalyst inlet operating temperature window of 300 C-450 C. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (2) The desulfurization procedure developed showed that six catalysts, which had been exposed to fuel sulfur levels of 3-, 16-, and 30-ppm for as long as 250 hours, could be recovered to greater than 85% NO(sub x) conversion efficiency over a catalyst inlet operating temperature window of 300 C-450 C, after a single desulfurization event. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (3) The desulfurization procedure developed has the potential to meet in-service engine operating conditions and provide acceptable driveability conditions. (4) Although aging with 78-ppm sulfur fuel reduced NO(sub x) conversion efficiency more than aging with 3-ppm sulfur fuel as a result of sulfur contamination, the desulfurization events restored the conversion efficiency to nearly the same level of performance. However, repeatedly exposing the catalyst to the desulfurization procedure developed in this program caused a continued decline in the catalyst's desulfurized performance. Additional work will be

  6. Studies on transfer phenomena of tritium from liquid to gaseous phase in a successive catalyst and ordered packing system

    International Nuclear Information System (INIS)

    Bornea, Anisia; Cristescu, Ion; Zamfirache, Marius; Varlam, Carmen

    2001-01-01

    The processes for hydrogen isotope separation are very important for nuclear technology. One of the most important processes in tritium separation, is the water-hydrogen catalytic isotope exchange. In a column of isotope exchange, tritium is transferred from the liquid phase (tritiated heavy water) to the gaseous phase (hydrogen). In the experimental set-up, which was used, the column of catalytic isotope exchange is filled with successive layers of catalyst Pt/C/PtFe and B7 type ordered packing of phosphor bronze. The tritium transfer from liquid phase to water vapours, is achieved on ordered packing by distillation process: (DTO)L+(D 2 O)V → (D 2 O)L+(DTO)V. On the catalytic tritium transfer from water vapours to hydrogen gas is achieved by the catalytic isotopic exchange process: (DTO)V+(D 2 )G → (D 2 O)V+(DT)G. We analyzed the transfer phenomena of tritium in this system by using the experimental data obtained. The mathematical model presented in the paper allowed computing experimental data for testing the catalyst performances. The transfer equations are solved using the Runge - Kutta method. In this way the speed constants which characterized the isotopic exchange on the catalysis bed ks, and the distillation on the ordered packing kd, were expressed as function of experimental concentrations and hydrodynamic conditions. (authors)

  7. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The mild liquid-phase synthesis of 3-picoline from acrolein diethyl acetal and ammonia over heterogeneous catalysts

    Science.gov (United States)

    Luo, Cai-Wu; Chao, Zi-Sheng; Lei, Bo; Wang, Hong; Zhang, Jun; Wang, Zheng-Hao

    2017-11-01

    The liquid-phase synthesis of 3-picoline from the reaction of acrolein diethyl acetal and ammonia over ion-exchanged resins (D402 and D002) and HZSM-5 (Si/Al = 25) was carried out in a batch reactor. Various influencing parameters, including by the addition of water, ion-exchanged resins, reaction temperature and HZSM-5, were systematically investigated. The results showed that the reaction could be directly conducted, and organic acid wasn’t utilized. The highest yield of 3-picoline reached up to 24% using HZSM-5 as catalyst at 110 °C.

  9. Next Generation Metallic Iron Nodule Technology in Electric Arc Steelmaking - Phase II

    Energy Technology Data Exchange (ETDEWEB)

    Donald R. Fosnacht; Iwao Iwasaki; Richard F. Kiesel; David J. Englund; David W. Hendrickson; Rodney L. Bleifuss

    2010-12-22

    -bituminous coal as a reductant. From over 4000 laboratory tube and box furnace tests, it was established that the correct combination of additives, fluxes, and reductant while controlling the concentration of CO and CO2 in the furnace atmosphere (a) lowers the operating temperature, (b) decreases the use of reductant coal (c) generates less micro nodules of iron, and (d) promotes desulphurization. The laboratory scale work was subsequently verified on 12.2 m (40 ft) long pilot scale furnace. High quality NRI could be produced on a routine basis using the pilot furnace facility with energy provided from oxy-gas or oxy-coal burner technologies. Specific strategies were developed to allow the use of sub-bituminous coals both as a hearth material and as part of the reaction mixture. Computational Fluid Dynamics (CFD) modeling was used to study the overall carbothermic reduction and smelting process. The movement of the furnace gas on a pilot hearth furnace and larger simulated furnaces and various means of controlling the gas atmosphere were evaluated. Various atmosphere control methods were identified and tested during the course of the investigation. Based on the results, the appropriate modifications to the furnace were made and tested at the pilot scale. A series of reduction and smelting tests were conducted to verify the utility of the processing conditions. During this phase, the overall energy use characteristics, raw materials, alternative fuels, and the overall economics predicted for full scale implementation were analyzed. The results indicate that it should be possible to lower reaction temperatures while simultaneously producing low sulfur, high carbon NRI if the right mix chemistry and atmosphere are employed. Recommendations for moving the technology to the next stage of commercialization are presented.

  10. Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

    OpenAIRE

    José da Silva, Márcio; Faria dos Santos, Lidiane

    2013-01-01

    A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by ace...

  11. Interactions between coherent twin boundaries and phase transition of iron under dynamic loading and unloading

    Science.gov (United States)

    Wang, Kun; Chen, Jun; Zhang, Xueyang; Zhu, Wenjun

    2017-09-01

    Phase transitions and deformation twins are constantly reported in many BCC metals under high pressure, whose interactions are of fundamental importance to understand the strengthening mechanism of these metals under extreme conditions. However, the interactions between twins and phase transition in BCC metals remain largely unexplored. In this work, interactions between coherent twin boundaries and α ↔ ɛ phase transition of iron are investigated using both non-equilibrium molecular dynamics simulations and the nudged elastic band method. Mechanisms of both twin-assisted phase transition and reverse phase transition are studied, and orientation relationships between BCC and HCP phases are found to be ⟨"separators="|11 1 ¯ ⟩ B C C||⟨"separators="|1 ¯2 1 ¯ 0 ⟩ H C P and ⟨"separators="|1 1 ¯ 0 ⟩ B C C||⟨"separators="|0001 ⟩ H C P for both cases. The twin boundary corresponds to {"separators="|10 1 ¯ 0 } H C P after the phase transition. It is amazing that the reverse transition seems to be able to "memorize" and recover the initial BCC twins. The memory would be partly lost when plastic slips take place in the HCP phase before the reverse transition. In the recovered initial BCC twins, three major twin spacings are observed, which are well explained in terms of energy barriers of transition from the HCP phase to the BCC twin. Besides, the variant selection rule of the twin assisted phase transition is also discussed. The results of present work could be expected to give some clues for producing ultra-fine grain structures in materials exhibiting martensitic phase transition.

  12. High pressure flow reactor for in situ X-ray absorption spectroscopy of catalysts in gas-liquid mixtures—A case study on gas and liquid phase activation of a Co-Mo/Al2O3 hydrodesulfurization catalyst

    NARCIS (Netherlands)

    van Haandel, L.; Hensen, E.J.M.; Weber, Th.

    2017-01-01

    An in situ characterization of heterogeneous catalysts under industrial operating conditions may involve high pressure and reactants in both the gas and the liquid phase. In this paper, we describe an in situ XAS flow reactor, which is suitable to operate under such conditions (pmax 20 bar, Tmax 350

  13. Irradiation-induced void evolution in iron: A phase-field approach with atomistic derived parameters

    International Nuclear Information System (INIS)

    Wang Yuan-Yuan; Ding Jian-Hua; Huang Shao-Song; Zhao Ji-Jun; Liu Wen-Bo; Ke Xiao-Qin; Wang Yun-Zhi; Zhang Chi

    2017-01-01

    A series of material parameters are derived from atomistic simulations and implemented into a phase field (PF) model to simulate void evolution in body-centered cubic (bcc) iron subjected to different irradiation doses at different temperatures. The simulation results show good agreement with experimental observations — the porosity as a function of temperature varies in a bell-shaped manner and the void density monotonically decreases with increasing temperatures; both porosity and void density increase with increasing irradiation dose at the same temperature. Analysis reveals that the evolution of void number and size is determined by the interplay among the production, diffusion and recombination of vacancy and interstitial. (paper)

  14. Mapping the Superconducting Anti-ferromagnetic C4 Phase in Iron-Pnictides

    Science.gov (United States)

    Stadel, Ryan; Taddei, Keith; Bugaris, Dan; Lapidus, Saul; Claus, Helmut; Phelan, Daniel; Chung, Duck Young; Kanatzidis, Mercouri; Osborn, Raymond; Rosenkranz, Stephan; Chmaissem, Omar

    Following the discovery of the microscopic coexistence of antifermagnetic spin density waves and superconductivity in Ba1-xKxFe2As2 and the low temperature re-entrance to the novel magnetic C4 tetragonal phase in Ba1-xNaxFe2As2, there has been significant interest in developing an understanding of the properties and formation of these phases and analyzing their dependence on temperature and composition in hole-doped 122 alkaline earth metal/iron-pnictides. We describe the mapping of various Ba, Sr, and Ca 122 phase diagrams with systematically controlled levels of hole-doping of alkaline metal onto the alkaline earth metal site, which was investigated via x-ray and neutron diffraction. Our elaborate synthesis, diffraction work, and analysis maps and firmly establishes the C4 phase space in these ternary diagrams as well as the boundary lines that separate the individual phases, and provides natural clues as well as a framework to investigate the stability and formation of the C4 domes that shift location with doping contents in the phase diagrams. Work at Argonne was supported by US DOE, Office of Science, Materials Sciences and Engineering Division.

  15. Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

    KAUST Repository

    Ladelta, Viko

    2018-03-16

    Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP4 promotes both intra- and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the “catalyst-switch” strategy [benzyl alcohol, t-BuP4/neutralization with diphenyl phosphate/(t-BuP2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.

  16. Block Copolymers of Macrolactones/Small Lactones by a “Catalyst-Switch” Organocatalytic Strategy. Thermal Properties and Phase Behavior

    KAUST Repository

    Ladelta, Viko; Kim, Joey D.; Bilalis, Panagiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

    2018-01-01

    Poly(macrolactones) (PMLs) can be considered as biodegradable alternatives of polyethylene; however, controlling the ring-opening polymerization (ROP) of macrolactone (ML) monomers remains a challenge due to their low ring strain. To overcome this problem, phosphazene (t-BuP4), a strong superbase, has to be used as catalyst. Unfortunately, the one-pot sequential block copolymerization of MLs with small lactones (SLs) is impossible since the high basicity of t-BuP4 promotes both intra- and intermolecular transesterification reactions, thus leading to random copolymers. By using ROP and the “catalyst-switch” strategy [benzyl alcohol, t-BuP4/neutralization with diphenyl phosphate/(t-BuP2)], we were able to synthesize different well-defined PML-b-PSL block copolymers (MLs: dodecalactone, ω-pentadecalactone, and ω-hexadecalactone; SLs: δ-valerolactone and ε-caprolactone). The thermal properties and the phase behavior of these block copolymers were studied by differential scanning calorimetry and X-ray diffraction spectroscopy. This study shows that the thermal properties and phase behavior of PMLs-b-PSLs are largely influenced by the PMLs block if PMLs components constitute the majority of the block copolymers.

  17. Intermetallic phases in the iron-rich region of the Zr-Fe phase diagram

    Energy Technology Data Exchange (ETDEWEB)

    Granovsky, M.S. [Comision Nacional de Energia Atomica, Buenos Aires (Argentina). Dept. de Materiales; Arias, D. [Comision Nacional de Energia Atomica, Buenos Aires (Argentina). Dept. de Materiales

    1996-04-01

    Intermetallic phases in the Fe-rich region of the Zr-Fe system are studied by X-ray diffraction and optical and electron microscopy. The chemical composition of each phase has been quantitatively measured in a electron microprobe. The stable phases found in this region are ZrFe{sub 2}, Zr{sub 6}Fe{sub 23} and ({alpha}Fe). ZrFe{sub 2} is identified as a cubic Laves type phase (C15) and the ZrFe{sub 2}/ZrFe{sub 2}+Zr{sub 6}Fe{sub 23} boundary composition is 73{+-}1 at.% Fe. Zr{sub 6}Fe{sub 23} is a cubic phase of the Th{sub 6}Mn{sub 23} type and its composition is 80.0{+-}1.5 at.% Fe. The eutectic L{r_reversible}Zr{sub 6}Fe{sub 23}+{tau}-Fe transformation temperature and composition are 1325 C and 91{+-}1 at.% Fe, respectively. The solubility of Zr in {tau}-Fe at 1012 C is 500{+-}50 appm and 1000{+-}100 appm close to the eutectic temperature. (orig.).

  18. Intermetallic phases in the iron-rich region of the Zr-Fe phase diagram

    International Nuclear Information System (INIS)

    Granovsky, M.S.; Arias, D.

    1996-01-01

    Intermetallic phases in the Fe-rich region of the Zr-Fe system are studied by X-ray diffraction and optical and electron microscopy. The chemical composition of each phase has been quantitatively measured in a electron microprobe. The stable phases found in this region are ZrFe 2 , Zr 6 Fe 23 and (αFe). ZrFe 2 is identified as a cubic Laves type phase (C15) and the ZrFe 2 /ZrFe 2 +Zr 6 Fe 23 boundary composition is 73±1 at.% Fe. Zr 6 Fe 23 is a cubic phase of the Th 6 Mn 23 type and its composition is 80.0±1.5 at.% Fe. The eutectic L↔Zr 6 Fe 23 +τ-Fe transformation temperature and composition are 1325 C and 91±1 at.% Fe, respectively. The solubility of Zr in τ-Fe at 1012 C is 500±50 appm and 1000±100 appm close to the eutectic temperature. (orig.)

  19. Supplementation of iron in pulmonary hypertension: Rationale and design of a phase II clinical trial in idiopathic pulmonary arterial hypertension

    Science.gov (United States)

    Howard, Luke S.G.E.; Watson, Geoffrey M.J.; Wharton, John; Rhodes, Christopher J.; Chan, Kakit; Khengar, Rajeshree; Robbins, Peter A.; Kiely, David G.; Condliffe, Robin; Elliott, Charlie A.; Pepke-Zaba, Joanna; Sheares, Karen; Morrell, Nicholas W.; Davies, Rachel; Ashby, Deborah; Gibbs, J. Simon R.; Wilkins, Martin R.

    2013-01-01

    Our aim is to assess the safety and potential clinical benefit of intravenous iron (Ferinject) infusion in iron deficient patients with idiopathic pulmonary arterial hypertension (IPAH). Iron deficiency in the absence of anemia (1) is common in patients with IPAH; (2) is associated with inappropriately raised levels of hepcidin, the key regulator of iron homeostasis; and (3) correlates with disease severity and worse clinical outcomes. Oral iron absorption may be impeded by reduced absorption due to elevated hepcidin levels. The safety and benefits of parenteral iron replacement in IPAH are unknown. Supplementation of Iron in Pulmonary Hypertension (SIPHON) is a Phase II, multicenter, double-blind, randomized, placebo-controlled, crossover clinical trial of iron in IPAH. At least 60 patients will be randomized to intravenous ferric carboxymaltose (Ferinject) or saline placebo with a crossover point after 12 weeks of treatment. The primary outcome will be the change in resting pulmonary vascular resistance from baseline at 12 weeks, measured by cardiac catheterization. Secondary measures include resting and exercise hemodynamics and exercise performance from serial bicycle incremental and endurance cardiopulmonary exercise tests. Other secondary measurements include serum iron indices, 6-Minute Walk Distance, WHO functional class, quality of life score, N-terminal pro-brain natriuretic peptide (NT-proBNP), and cardiac anatomy and function from cardiac magnetic resonance. We propose that intravenous iron replacement will improve hemodynamics and clinical outcomes in IPAH. If the data supports a potentially useful therapeutic effect and suggest this drug is safe, the study will be used to power a Phase III study to address efficacy. PMID:23662181

  20. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Zhipan [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Zhang, Yalei, E-mail: zhangyalei@tongji.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Dai, Chaomeng [College of Civil Engineering, Tongji University, Shanghai 200092 (China); Sun, Zhen [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)

    2015-04-28

    Highlights: • MMIC with large surface area and pore volume was synthesized via the hard template. • MMIC could be easily separated from aqueous solution with an external magnetic field. • MMIC presented excellent catalytic activity for the oxidation of As(III). • As(III) was mainly oxidized by surface-bound ·OH{sub ads} and free ·OH{sub free} radicals. • MMIC played a dual function role for the arsenic removal in aqueous solution. - Abstract: Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000 ppb As(III) after 60 min and complete removal of arsenic species after 180 min with reaction conditions of 0.4 g/L catalyst, pH of 3.0 and 0.4 mM H{sub 2}O{sub 2}. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014 min{sup −1} to 0.0548 min{sup −1} as the H{sub 2}O{sub 2} concentration increased from 0.04 mM to 0.4 mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by ·OH radicals, including the surface-bound ·OH{sub ads} generated on the MMIC surface which were involved in ≡Fe{sup 2+} and ≡Ce{sup 3+}, and free ·OH{sub free} generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption.

  1. Quantitative EPMA of Nano-Phase Iron-Silicides in Apollo 16 Lunar Regolith

    Science.gov (United States)

    Gopon, P.; Fournelle, J.; Valley, J. W.; Pinard, P. T.; Sobol, P.; Horn, W.; Spicuzza, M.; Llovet, X.; Richter, S.

    2013-12-01

    Until recently, quantitative EPMA of phases under a few microns in size has been extremely difficult. In order to achieve analytical volumes to analyze sub-micron features, accelerating voltages between 5 and 8 keV need to be used. At these voltages the normally used K X-ray transitions (of higher Z elements) are no longer excited, and we must rely of outer shell transitions (L and M). These outer shell transitions are difficult to use for quantitative EPMA because they are strongly affected by different bonding environments, the error associated with their mass attenuation coefficients (MAC), and their proximity to absorption edges. These problems are especially prevalent for the transition metals, because of the unfilled M5 electron shell where the Lα transition originates. Previous studies have tried to overcome these limitations by using standards that almost exactly matched their unknowns. This, however, is cumbersome and requires accurate knowledge of the composition of your sample beforehand, as well as an exorbitant number of well characterized standards. Using a 5 keV electron beam and utilizing non-standard X-ray transitions (Ll) for the transition metals, we are able to conduct accurate quantitative analyses of phases down to ~300nm. The Ll transition in the transition metals behaves more like a core-state transition, and unlike the Lα/β lines, is unaffected by bonding effects and does not lie near an absorption edge. This allows for quantitative analysis using standards do not have to exactly match the unknown. In our case pure metal standards were used for all elements except phosphorus. We present here data on iron-silicides in two Apollo 16 regolith grains. These plagioclase grains (A6-7 and A6-8) were collected between North and South Ray Craters, in the lunar highlands, and thus are associated with one or more large impact events. We report the presence of carbon, nickel, and phosphorus (in order of abundance) in these iron-silicide phases

  2. Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

    Science.gov (United States)

    Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

    2018-02-27

    The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

  3. Investigation of phase transformations in ductile cast iron of differential scanning calorimetry

    International Nuclear Information System (INIS)

    Przeliorz, R; Piatkowski, J

    2011-01-01

    The effect of heating rate on phase transformations to austenite range in ductile cast iron of the EN-GJS-450-10 grade was investigated. For studies of phase transformations, the technique of differential scanning calorimetry (DSC) was used. Micro structure was examined by optical microscopy. The calorimetric examinations have proved that on heating three transformations occur in this grade of ductile iron, viz. magnetic transformation at the Curie temperature, pearlite→austenite transformation and ferrite→austenite transformation. An increase in the heating rate shifts the pearlite→austenite and ferrite→austenite transformations to higher temperature range. At the heating rate of 5 and 15 deg. C min -1 , local extrema have been observed to occur: for pearlite→austenite transformation at 784 deg. C and 795 deg. C, respectively, and for ferrite+ graphite →austenite transformation at 805 deg. C and 821 deg. C, respectively. The Curie temperature of magnetic transformation was extrapolated to a value of 740 deg. C. Each transformation is related with a specific thermal effect. The highest value of enthalpy is accompanying the ferrite→austenite transformation, the lowest occurs in the case of pearlite→austenite transformation.

  4. Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

    Energy Technology Data Exchange (ETDEWEB)

    Deshmukh, Ruchi; Mehra, Anurag; Thaokar, Rochish, E-mail: rochish@che.iitb.ac.in [Indian Institute of Technology-Bombay, Department of Chemical Engineering (India)

    2017-01-15

    Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra-methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe {sub 3}O{sub 4}) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe {sub 3}O{sub 4}) or a mixture of (γ-Fe {sub 2}O{sub 3} + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 {sup ∘}C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.

  5. Single-step gas phase synthesis of stable iron aluminide nanoparticles with soft magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Vernieres, Jerome, E-mail: Jerome.vernieres@oist.jp; Benelmekki, Maria; Kim, Jeong-Hwan; Grammatikopoulos, Panagiotis; Diaz, Rosa E. [Nanoparticles by Design Unit, Okinawa Institute of Science and Technology (OIST) Graduate University, 1919-1 Tancha, Onna Son, Okinawa 904-0495 (Japan); Bobo, Jean-François [Centre d’Elaboration de Materiaux et d’Etudes Structurales (CEMES), 29 rue Jeanne Marvig, 31055 Toulouse Cedex 4 (France); Sowwan, Mukhles, E-mail: Mukhles@oist.jp [Nanoparticles by Design Unit, Okinawa Institute of Science and Technology (OIST) Graduate University, 1919-1 Tancha, Onna Son, Okinawa 904-0495 (Japan); Nanotechnology Research Laboratory, Al-Quds University, P.O. Box 51000, East Jerusalem, Palestine (Country Unknown)

    2014-11-01

    Soft magnetic alloys at the nanoscale level have long generated a vivid interest as candidate materials for technological and biomedical purposes. Consequently, controlling the structure of bimetallic nanoparticles in order to optimize their magnetic properties, such as high magnetization and low coercivity, can significantly boost their potential for related applications. However, traditional synthesis methods stumble upon the long standing challenge of developing true nanoalloys with effective control over morphology and stability against oxidation. Herein, we report on a single-step approach to the gas phase synthesis of soft magnetic bimetallic iron aluminide nanoparticles, using a versatile co-sputter inert gas condensation technique. This method allowed for precise morphological control of the particles; they consisted of an alloy iron aluminide crystalline core (DO{sub 3} phase) and an alumina shell, which reduced inter-particle interactions and also prevented further oxidation and segregation of the bimetallic core. Remarkably, the as-deposited alloy nanoparticles show interesting soft magnetic properties, in that they combine a high saturation magnetization (170 emu/g) and low coercivity (less than 20 Oe) at room temperature. Additional functionality is tenable by modifying the surface of the particles with a polymer, to ensure their good colloidal dispersion in aqueous environments.

  6. Application of Differential Scanning Calorimetry (DSC in study of phase transformations in ductile iron

    Directory of Open Access Journals (Sweden)

    R. Przeliorz

    2010-04-01

    Full Text Available The effect of heating rate on phase transformations to austenite range in ductile iron of the EN-GJS-450-10 grade was investigated. For studies of phase transformations, the technique of differential scanning calorimetry (DSC was used. Microstructure was examined by optical microscopy. The calorimetric examinations have proved that on heating three transformations occur in this grade of ductile iron, viz. magnetic transformation at the Curie temperature, pearlite→austenite transformation and ferrite→austenite transformation. An increase in the heating rate shifts the pearlite→austenite and ferrite→austenite transformations to higher temperature range. At the heating rate of 5 and 15°C/min, local extrema have been observed to occur: for pearlite→austenite transformation at 784°C and 795°C, respectively, and for ferrite→austenite transformation at 805°C and 821°C, respectively. The Curie temperature of magnetic transformation was extrapolated to a value of 740°C. Each transformation is related with a specific thermal effect. The highest value of enthalpy is accompanying the ferrite→austenite transformation, the lowest occurs in the case of pearlite→austenite transformation.

  7. Role of multiorbital effects in the magnetic phase diagram of iron pnictides

    Science.gov (United States)

    Christensen, Morten H.; Scherer, Daniel D.; Kotetes, Panagiotis; Andersen, Brian M.

    2017-07-01

    We elucidate the pivotal role of the band structure's orbital content in deciding the type of commensurate magnetic order stabilized within the itinerant scenario of iron pnictides. Recent experimental findings in the tetragonal magnetic phase attest to the existence of the so-called charge and spin ordered density wave over the spin-vortex crystal phase, the latter of which tends to be favored in simplified band models of itinerant magnetism. Here we show that employing a multiorbital itinerant Landau approach based on realistic band structures can account for the experimentally observed magnetic phase, and thus shed light on the importance of the orbital content in deciding the magnetic order. In addition, we remark that the presence of a hole pocket centered at the Brillouin zone's M point favors a magnetic stripe rather than a tetragonal magnetic phase. For inferring the symmetry properties of the different magnetic phases, we formulate our theory in terms of magnetic order parameters transforming according to irreducible representations of the ensuing D4 h point group. The latter method not only provides transparent understanding of the symmetry-breaking schemes but also reveals that the leading instabilities always belong to the {A1 g,B1 g} subset of irreducible representations, independently of their C2 or C4 nature.

  8. FY 1980 Report on results of Sunshine Project. Research and development of coal liquefaction techniques (Development of direct hydrogenation type liquefaction plant and researches on liquefaction reactions in the presence of iron-based catalyst); 1980 nendo sekitan ekika gijutsu no kenkyu kaihatsu, chokusetsu suiten ekika plant no kaihatsu seika hokokusho. Tetsukei shokubai ni yoru ekika hanno no kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1981-03-01

    This program is aimed at development of iron-based catalyst suited for direct hydrogenation type coal liquefaction by elucidating the effects of the catalyst on the liquefaction reactions. The iron-based catalyst seems to act as the radical stabilizer rather than the reaction promoter, because the increased quantity of the catalyst and increased H{sub 2} pressure share the common pattern rather than the catalyst enhances the activity, which is associated with increased reaction temperature or residence time. This is more notably observed when the coal species is changed to brown coal. In other words, recombination of the decomposition products by polycondensation is accelerated in the presence of the catalyst in decomposition of brown coal from bituminous coal, with the result that the catalyst effects are more notably observed. Whether this results from difference in age between brown coal and bituminous coal or content of specific types of ashes should be elucidated, because this point is considered to deeply relate to eventual development of the liquefaction reaction system. The FY 1980 program includes the primary screening of different types of iron compounds and tests of some iron-metal-based catalysts. (NEDO)

  9. Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

    Energy Technology Data Exchange (ETDEWEB)

    Kasakov, Stanislav; Zhao, Chen; Barath, Eszter; Chase, Zizwe A.; Fulton, John L.; Camaioni, Donald M.; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A.

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanol in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.

  10. Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

    Science.gov (United States)

    Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis of 3D iron and carbon-based composite as a bifunctional sorbent and catalyst for remediation of organic pollutants

    Science.gov (United States)

    Li, Ling; Shen, Yi; Wang, Zhaomei

    2017-07-01

    We prepared a 3D monolith by integrating graphite nanosheet encapsulated iron nanoparticles (Fe@GNS) into graphite felt (GF) supports. The structural properties of the resulting Fe@GNS/GF monolith are characterized by x-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy and N2 adsorption-desorption isotherms. The Fe@GNS/GF monoliths are utilized as a bifunctional sorbent and catalyst for water remediation. Using Congo red and methyl violet 2B as model pollutants, the sorption and catalytic performance of the Fe@GNS/GF composite are examined. The Fe@GNS/GF monolith possesses maximum sorption capacities of 177 and 142 mg g-1 for the sorption of CR and MV-2B, respectively. It also exhibits rate constants of 0.0563 and 0.0464 min-1 for the catalytic degradation of CR and MV-2B, respectively. As a proof of concept, the Fe@GNS/GF is successfully utilized to decontaminate simulated organic waste water via a combination of sorption and catalytic degradation processes.

  12. Study on the Microstructure and Liquid Phase Formation in a Semisolid Gray Cast Iron

    Science.gov (United States)

    Benati, Davi Munhoz; Ito, Kazuhiro; Kohama, Kazuyuki; Yamamoto, Hajime; Zoqui, Eugenio José

    2017-10-01

    The development of high-quality semisolid raw materials requires an understanding of the phase transformations that occur as the material is heated up to the semisolid state, i.e., its melting behavior. The microstructure of the material plays a very important role during semisolid processing as it determines the flow behavior of the material when it is formed, making a thorough understanding of the microstructural evolution essential. In this study, the phase transformations and microstructural evolution in Fe2.5C1.5Si gray cast iron specially designed for thixoforming processes as it was heated to the semisolid state were observed using in situ high-temperature confocal laser scanning microscopy. At room temperature, the alloy has a matrix of pearlite and ferrite with fine interdendritic type D flake graphite. During heating, the main transformations observed were graphite precipitation inside the grains and at the austenite grain boundaries; graphite flakes and graphite precipitates growing and becoming coarser with the increasing temperature; and the beginning of melting at around 1413 K to 1423 K (1140 °C to 1150 °C). Melting begins with the eutectic phase ( i.e., the carbon-rich phase) and continues with the primary phase (primary austenite), which is consumed as the temperature increases. Melting of the eutectic phase composed by coarsened interdendritic graphite flakes produced a semi-continuous liquid network homogeneously surrounding and wetting the dendrites of the solid phase, causing grains to detach from each other and producing the intended solid globules immersed in liquid.

  13. A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

    International Nuclear Information System (INIS)

    Fife, K.W.

    1996-09-01

    Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of ∼ 100 C. In spite of these aggressive conditions, PuO 2 dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 microm) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions

  14. Modified iron oxide nanomaterials: Functionalization and application

    International Nuclear Information System (INIS)

    Bagheri, Samira; Julkapli, Nurhidayatullaili Muhd

    2016-01-01

    Iron oxide magnetic nanoparticles have aroused the interest of researchers of materials' chemistry due to its exceptional properties such as decent magnetic, electric, catalytic, biocompatibility, and low toxicity. However, these magnetic nanoparticles are predisposed towards aggregation and forming larger particles, due to its strong anisotropic dipolar interactions, particularly in the aqueous phase, consequently depriving them of dispersibility and particular properties, ultimately degrading their performance. Hence, this review focuses on modified magnetic nanoparticles that are stable, easily synthesized, possess a high surface area and could be facile-separated via magnetic forces, and are of low toxicity and costs for applications such as catalyst/catalyst support, food security, biomedical, and pollutant remediation. - Highlights: • Nanomagnetite is interesting due to its exceptional properties. • Nanomagnetite is predisposed towards aggregation and forming larger particles. • Modified nanomagnetite are stable, easily synthesized, possess high surface area. • Modified nanomagnetite got applications as catalyst/catalyst support.

  15. Modified iron oxide nanomaterials: Functionalization and application

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, Samira; Julkapli, Nurhidayatullaili Muhd

    2016-10-15

    Iron oxide magnetic nanoparticles have aroused the interest of researchers of materials' chemistry due to its exceptional properties such as decent magnetic, electric, catalytic, biocompatibility, and low toxicity. However, these magnetic nanoparticles are predisposed towards aggregation and forming larger particles, due to its strong anisotropic dipolar interactions, particularly in the aqueous phase, consequently depriving them of dispersibility and particular properties, ultimately degrading their performance. Hence, this review focuses on modified magnetic nanoparticles that are stable, easily synthesized, possess a high surface area and could be facile-separated via magnetic forces, and are of low toxicity and costs for applications such as catalyst/catalyst support, food security, biomedical, and pollutant remediation. - Highlights: • Nanomagnetite is interesting due to its exceptional properties. • Nanomagnetite is predisposed towards aggregation and forming larger particles. • Modified nanomagnetite are stable, easily synthesized, possess high surface area. • Modified nanomagnetite got applications as catalyst/catalyst support.

  16. Iron and Immunity

    NARCIS (Netherlands)

    Verbon, E.H.|info:eu-repo/dai/nl/413534049; Trapet, P.L.; Stringlis, I.|info:eu-repo/dai/nl/41185206X; Kruijs, Sophie; Bakker, P.A.H.M.|info:eu-repo/dai/nl/074744623; Pieterse, C.M.J.|info:eu-repo/dai/nl/113115113

    2017-01-01

    Iron is an essential nutrient for most life on Earth because it functions as a crucial redox catalyst in many cellular processes. However, when present in excess iron can lead to the formation of harmful hydroxyl radicals. Hence, the cellular iron balance must be tightly controlled. Perturbation of

  17. Esterification of oleic acid in a three-phase, fixed-bed reactor packed with a cation exchange resin catalyst.

    Science.gov (United States)

    Son, Sung Mo; Kimura, Hiroko; Kusakabe, Katsuki

    2011-01-01

    Esterification of oleic acid was performed in a three-phase fixed-bed reactor with a cation exchange resin catalyst (Amberlyst-15) at high temperature, which was varied from 80 to 120 °C. The fatty acid methyl ester (FAME) yields in the fixed-bed reactor were increased with increases in the reaction temperature, methanol flow rate and bed height. Moreover, the FAME yields were higher than those obtained using a batch reactor due to an equilibrium shift toward the product that resulted from continuous evaporation of the produced water. In addition, there was no catalyst deactivation during the esterification of oleic acid. However, addition of sunflower oil to the oleic acid reduced the FAME yield obtained from simultaneous esterification and transesterification. The FAME yield was 97.5% at a reaction temperature of 100 °C in the fixed-bed with a height of 5 cm when the methanol and oleic acid feed rates were 8.6 and 9.0 mL/h, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

  18. Phase stability of iron germanate, FeGeO3, to 127 GPa

    Science.gov (United States)

    Dutta, R.; Tracy, S. J.; Stan, C. V.; Prakapenka, V. B.; Cava, R. J.; Duffy, T. S.

    2018-04-01

    The high-pressure behavior of germanates is of interest as these compounds serve as analogs for silicates of the deep Earth. Current theoretical and experimental studies of iron germanate, FeGeO3, are limited. Here, we have examined the behavior of FeGeO3 to 127 GPa using the laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. Upon compression at room temperature, the ambient-pressure clinopyroxene phase transforms to a disordered triclinic phase [FeGeO3 (II)] at 18 GPa in agreement with earlier studies. An additional phase transition to FeGeO3 (III) occurs above 54 GPa at room temperature. Laser-heating experiments ( 1200-2200 K) were conducted at three pressures (33, 54, and 123 GPa) chosen to cover the stability regions of different GeO2 polymorphs. In all cases, we observe that FeGeO3 dissociates into GeO2 + FeO at high pressure and temperature conditions. Neither the perovskite nor the post-perovskite phase was observed up to 127 GPa at ambient or high temperatures. The results are consistent with the behavior of FeSiO3, which also dissociates into a mixture of the oxides (FeO + SiO2) at least up to 149 GPa.

  19. Role of a gas phase in the kinetics of zinc and iron reduction with carbon from slag melts

    Science.gov (United States)

    Chumarev, V. M.; Selivanov, E. N.

    2013-03-01

    The influence of the mass transfer conditions in the gas phase having formed at the carbon-slag melt interface on CO regeneration is approximately estimated in the framework of a two-stage scheme of metal reduction from slag melts by carbon. The effect of zinc vapors on the combined reduction of iron and zinc from slags is considered. The influence of the slag composition and temperature on the critical concentration of zinc oxide above which no iron forms as an individual phase is explained.

  20. Investigation of effects of boron additives and heat treatment on carbides and phase transition of highly alloyed duplex cast iron

    International Nuclear Information System (INIS)

    Tasgin, Yahya; Kaplan, Mehmet; Yaz, Mehmet

    2009-01-01

    The effect of boron additives and heat treatment on the microstructural morphology of the transition zone in a duplex cast iron, which has an outer shell of white cast iron (with a high Cr-content and containing boron additives) and an inner side composed of normal gray cast iron, has been investigated. For this purpose, two experimental materials possessing different compositions of white-gray duplex cast iron were produced. Subsequently, metallographic investigations were carried out to study the effect of heat treatment applied to the experimental materials by using the scanning electron microscopy technique, along with optical microscopy and energy dispersive X-ray spectroscopy. Moreover, the formation of various phases and carbide composites in the samples and their effects on the hardness were also investigated using X-ray diffraction techniques. The results of investigations, and hardness showed that addition of the elements Cr and B to high-alloyed white cast iron affected carbide formation significantly, while simultaneously hardening the microstructure, and consequently the carbide present in the transition area of white-gray cast iron was spread out and became thinner. However, B additives and heat treatment did not cause any damage to the transition region of high Cr-content duplex cast iron.

  1. Controlled formation of iron carbides and their performance in Fischer-Tropsch synthesis

    KAUST Repository

    Wezendonk, Tim A.

    2018-04-19

    Iron carbides are unmistakably associated with the active phase for Fischer-Tropsch synthesis (FTS). The formation of these carbides is highly dependent on the catalyst formulation, the activation method and the operational conditions. Because of this highly dynamic behavior, studies on active phase performance often lack the direct correlation between catalyst performance and iron carbide phase. For the above reasons, an extensive in situ Mössbauer spectroscopy study on highly dispersed Fe on carbon catalysts (Fe@C) produced through pyrolysis of a Metal Organic Framework was coupled to their FTS performance testing. The preparation of Fe@C catalysts via this MOF mediated synthesis allows control over the active phase formation and therefore provides an ideal model system to study the performance of different iron carbides. Reduction of fresh Fe@C followed by low-temperature Fischer-Tropsch (LTFT) conditions resulted in the formation of the ε′-Fe2.2C, whereas carburization of the fresh catalysts under high-temperature Fischer-Tropsch (HTFT) resulted in the formation of χ-Fe5C2. Furthermore, the different activation methods did not alter other important catalyst properties, as pre- and post-reaction transmission electron microscopy (TEM) characterization confirmed that the iron nanoparticle dispersion was preserved. The weight normalized activities (FTY) of χ-Fe5C2 and ε′-Fe2.2C are virtually identical, whilst it is found that ε′-Fe2.2C is a better hydrogenation catalyst than χ-Fe5C2. The absence of differences under subsequent HTFT experiments, where χ-Fe5C2 is the dominating phase, is a strong indication that the iron carbide phase is responsible for the differences in selectivity.

  2. Catalysts for liquid phase oxidation of olefins and sulfur compounds; Catalyseurs pour l'oxydation en phase liquide d'olefines et de composes soufres

    Energy Technology Data Exchange (ETDEWEB)

    Palomeque Santiago, J.F.

    2002-07-01

    Several basic, acid and acid-base catalysts were studied for the epoxidation of olefins activated or not and dibenzo-thiophene.Hydrotalcite activation by thermic treatment and in situ re-hydration improves catalytic activity for 2-cyclohexene-1-one and isophorone. Bronsted basic sites were found to be more active than Lewis sites. Total conversion of 2-cyclohexene-1-one is reached in 1.5 h in polar solvents. W{sub 7}O{sub 24}{sup 6-} Iso-poly-anion was exchanged onto a meixnerite by a new preparation method, A meso-porous solid was obtained with good catalytic properties for cyclohexene epoxidation 100% selective to epoxide. W{sub 7}O{sub 24}{sup 6-} and WO{sub 5}{sup 2-} anions and phenyl and dodecyl-phospho-tungstates were grafted on hydrotalcites. Due to the acid-base characteristics of these solid catalysts, cyclohexene yields products of allylic reactions. Mg-La, and Mg-Al-La mixed oxides were synthesized and mixed phases were gotten. Their basic characteristics account for hydrogen peroxide decomposition which prevents DBT oxidation reaction to sulfone. On the contrary, Mg-Al re-hydrated hydrotalcites are very active for this reaction and remove 100% of sulfur compounds in 1 hour. New catalyst W-ZrO{sub 2} were synthesized with high acid properties. stable structure with temperature and high DBT conversion in less than 5 minutes of reaction. These catalytic systems can be applied for hydrocarbon desulfurization of fuels like naphtha, gas oil and kerosene. (author)

  3. Rapid Separation of Copper Phase and Iron-Rich Phase From Copper Slag at Low Temperature in a Super-Gravity Field

    Science.gov (United States)

    Lan, Xi; Gao, Jintao; Huang, Zili; Guo, Zhancheng

    2018-06-01

    A novel approach for quickly separating a metal copper phase and iron-rich phase from copper slag at low temperature is proposed based on a super-gravity method. The morphology and mineral evolution of the copper slag with increasing temperature were studied using in situ high-temperature confocal laser scanning microscopy and ex situ scanning electron microscopy and X-ray diffraction methods. Fe3O4 particles dispersed among the copper slag were transformed into FeO by adding an appropriate amount of carbon as a reducing agent, forming the slag melt with SiO2 at low temperature and assisting separation of the copper phase from the slag. Consequently, in a super-gravity field, the metallic copper and copper matte were concentrated as the copper phase along the super-gravity direction, whereas the iron-rich slag migrated in the opposite direction and was quickly separated from the copper phase. Increasing the gravity coefficient (G) significantly enhanced the separation efficiency. After super-gravity separation at G = 1000 and 1473 K (1200 °C) for 3 minutes, the mass fraction of Cu in the separated copper phase reached 86.11 wt pct, while that in the separated iron-rich phase was reduced to 0.105 wt pct. The recovery ratio of Cu in the copper phase was as high as up to 97.47 pct.

  4. KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

    Directory of Open Access Journals (Sweden)

    Mohammad Sadiq

    2015-08-01

    Full Text Available Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68% and selectivity (100% for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

  5. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    International Nuclear Information System (INIS)

    Mahdavi, Vahid; Soleimani, Shima

    2014-01-01

    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

  6. Synthesis and characterization of conditioned carbon with iron nanoparticles for the arsenic removal in aqueous phase

    International Nuclear Information System (INIS)

    Flores C, D. O.

    2012-01-01

    Using pineapple husks conditioned with carboxymethylcellulose, hexamine and ferric nitrate, a carbonaceous material was obtained with nanoparticles of Fe (C Fe), which was characterized and tested for arsenic removal in the aqueous phase. The microscopic study showed spheres 4 microns and filaments 100 nm wide, so as iron particles whose diameter decreases to an average of 38.81 nm, when pyrolysis time was increased to 180 min. their distribution in the carbonaceous matrix is homogeneous. According to energy dispersive X-ray spectroscopy, C Fe contains C (82.29%), O (7.23%), K (0.68%), Ca (3.77%) and Fe (6.25%) and its diffraction pattern shows the characteristic peak of Fe (0), which is not observed in the coal without iron. By neutron activation analysis were quantified Al, Br, Ce, Co, Cr, Cs, Eu, Hf, K, Mg, Mn, Na, Rb, Sb, Sc and Zn, they can be involved in the process of sorption of As (v) forming surface active sites. For C Fe and C B characterized by Fourier transform infrared spectrometry, groups C-H, C=O, C=C, -Nh, NH 2 , isocyanate and isonitrile were found, the last two were formed by the present hexamine. X-ray photoelectron spectroscopy showed energy states of C 1 and O 1 in pineapple shell washed, shell conditioned with iron, C Fe at different times and the pyrolysis coal without iron (C B). The material C Fe 180 presented a specific area of 167 m 2 /g and 7.12 ± 1 sites/nm 2 isoelectric point while pH i = 11.1 C B is 98.80 m 2 /g specific area and 1.5 ± 1 sites/nm 2 and pH i = 10.6, being favorable to the sorption process. The highest removal of As(v) for both materials was at ph = 2, fitting the kinetic data to pseudo-second order model. The isotherms as a function of concentration were adjusted to Freundlich model indicating multilayer chemisorption at specific sites of a heterogeneous medium. Characterization by scanning electron microscopy after the sample sorption Fe nanoparticles remain in the carbonaceous matrix being not affected by the

  7. Synthesis and characterization of polystyrene coated iron oxide nanoparticles and asymmetric assemblies by phase inversion

    KAUST Repository

    Xie, Yihui

    2014-09-02

    Films with a gradient concentration of magnetic iron oxide nanoparticles are reported, based on a phase inversion membrane process. Nanoparticles with ∼13 nm diameter were prepared by coprecipitation in aqueous solution and stabilized by oleic acid. They were further functionalized by ATRP leading to grafted polystyrene brush. The final nanoparticles of 33 nm diameter were characterized by TGA, FTIR spectroscopy, GPC, transmission electron microscopy, and dynanmic light scattering. Asymmetric porous nanoparticle assemblies were then prepared by solution casting and immersion in water. The nanocomposite film production with functionalized nanoparticles is fast and technically scalable. The morphologies of films were characterized by scanning electron microscopy and atomic force microscopy, demonstrating the presence of sponge-like structures and finger-like cavities when 50 and 13 wt % casting solutions were, respectively, used. The magnetic properties were evaluated using vibrating sample magnetometer.

  8. Phase change of iron ore reduction process using EFB as reducing agent at 900-1200°C

    Science.gov (United States)

    Purwanto, H.; Salleh, H. M.; Rozhan, A. N.; Mohamad, A. S.; Zakiyuddin, A.

    2018-04-01

    Treatment of low grade iron ore involved reduction of oxygen in iron oxide by using reductant such as carbon monoxide or hydrogen gas. Presently, carboneous materials such as coke/coal are widely used as a source to provide reducing gas, but some problem arises from this material as the gas can harm the environments. Therefore, empty fruit bunch biomass from oil palm becomes an alternative to replace the usage of coke/coal as their major composition is carbon and hydrogen. The idea of replacing coke with biomass will reduce the amount of carbon dioxide release as biomass is a carbon neutral and renewable source, and at the same time abundance of waste from oil palm industries can be overcome. Therefore, the aim of this research is to upgrade the low grade iron with reducibility more than 50% being used in iron and steel making. In this research, low grade iron ore are mixed together with EFB then is making into composite pellet before being reduced at certain parameter chosen. The variables involved in this research is composition EFB (10%, 30% and 50%), temperature (1000°C, 1100°C and 1200°C) and reduction time is fixed with 30 minutes. From the experiment conducted, the highest reducibility achieved is 76.37% at temperature 1200°C. While XRD analysis shows the existence of metallic iron phase started to form at 1000°C with composition of 30% of EFB. Meanwhile, from magnetization test show that at 1200°C the highest magnetic susceptibility is achieved as the dominance phase at 1200°C is metallic phase. Therefore it is an interesting alternative to replace coke with biomass for reducing agent in upgrading low grade iron into workable ores.

  9. Orbital-selective Mott phase of Cu-substituted iron-based superconductors

    International Nuclear Information System (INIS)

    Liu, Yang; Zhao, Yang-Yang; Song, Yun

    2016-01-01

    We study the phase transition in Cu-substituted iron-based superconductors with a new developed real-space Green’s function method. We find that Cu substitution has strong effect on the orbital-selective Mott transition introduced by the Hund’s rule coupling. The redistribution of the orbital occupancy which is caused by the increase of the Hund’s rule coupling, gives rise to the Mott–Hubbard metal-insulator transition in the half-filled d xy orbital. We also find that more and more electronic states appear inside that Mott gap of the d xy orbital with the increase of Cu substitution, and the in-gap states around the Fermi level are strongly localized at some specific lattice sites. Further, a distinctive phase diagram, obtained for the Cu-substituted Fe-based superconductors, displays an orbital-selective insulating phase, as a result of the cooperative effect of the Hund’s rule coupling and the impurity-induced disorder. (paper)

  10. Uniformly active phase loaded selective catalytic reduction catalysts (V{sub 2}O{sub 5}/TNTs) with superior alkaline resistance performance

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Haiqiang; Wang, Penglu [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China); Chen, Xiongbo [South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou 510655 (China); Wu, Zhongbiao, E-mail: zbwu@zju.edu.cn [Key Laboratory of Environment Remediation and Ecological Health, Ministry of Education, College of Environmental & Resources Science, Zhejiang University, 310058 Hangzhou (China); Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027 (China)

    2017-02-15

    Highlights: • VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}. • Ion-exchange reaction occurs between VOSO{sub 4} and titanate nanotubes. • Ion-exchange resulting in uniformly vanadium distribution on titanate nanotubes. • VOSO{sub 4}-based catalyst exhibited impressive SCR activity and alkaline resistance. - Abstract: In this work, protonated titanate nanotubes was performed as a potential useful support and different vanadium precursors (NH{sub 4}VO{sub 3} and VOSO{sub 4}) were used to synthesize deNO{sub x} catalysts. The results showed that VOSO{sub 4} exhibited better synergistic effect with titanate nanotubes than NH{sub 4}VO{sub 3}, which was caused by the ion-exchange reaction. Then high loading content of vanadium, uniformly active phase distribution, better dispersion of vanadium, more acid sites, better V{sup 5+}/V{sup 4+} redox cycles and superior oxygen mobility were achieved. Besides, VOSO{sub 4}-based titanate nanotubes catalysts also showed enhanced alkaline resistance than particles (P25) based catalysts. It was strongly associated with its abundant acid sites, large surface area, flexible redox cycles and oxygen transfer ability. For the loading on protonated titanate nanotubes, active metal with cation groups was better precursors than anion ones. V{sub 2}O{sub 5}/TNTs catalyst was a promising substitute for the commercial vanadium catalysts and the work conducted herein provided a useful idea to design uniformly active phase loaded catalyst.

  11. Non-PGM cell catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Elvington, M. [Savannah River Consulting, Aiken, SC (United States); Ganesan, P. [Savannah River Consulting, Aiken, SC (United States)

    2017-09-27

    A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFCs. Iron based functionalities have been engineered into a variety of catalysts to evaluate their impact on activity for the ORR. A series of high surface area catalysts were synthesized and the impact of the chemical structure on the electrochemical and electrocatalytic properties was investigated. Elemental and surface analyses of the prepared catalysts reveal the incorporation of iron in a targeted and controlled manner. A high surface area framework catalyst was prepared that shows exceptional activity, comparable to state-of-the-art materials. The results of this research project provided critical seed data for the newly awarded ElectroCat project, which focuses on rationally designed framework catalysts for the oxygen reduction reaction.

  12. Effect of Al doping on phase formation and thermal stability of iron nitride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Tayal, Akhil [Amity Center for Spintronic Materials, Amity University, Sector 125, Noida 201 303 (India); Gupta, Mukul, E-mail: mgupta@csr.res.in [Amity Center for Spintronic Materials, Amity University, Sector 125, Noida 201 303 (India); Pandey, Nidhi [Amity Center for Spintronic Materials, Amity University, Sector 125, Noida 201 303 (India); Gupta, Ajay [UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore 452 001 (India); Horisberger, Michael [Laboratory for Developments and Methods, Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Stahn, Jochen [Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland)

    2015-11-25

    In the present work, we systematically studied the effect of Al doping on the phase formation of iron nitride (Fe–N) thin films. Fe–N thin films with different concentration of Al (Al = 0, 2, 3, 6, and 12 at.%) were deposited using dc magnetron sputtering by varying the nitrogen partial pressure between 0 and 100%. The structural and magnetic properties of the films were studied using x-ray diffraction and polarized neutron reflectivity. It was observed that at the lowest doping level (2 at.% of Al), nitrogen rich non-magnetic Fe–N phase gets formed at a lower nitrogen partial pressure as compared to the un-doped sample. Interestingly, we observed that as Al doping is increased beyond 3 at.%, nitrogen rich non-magnetic Fe–N phase appears at higher nitrogen partial pressure as compared to un-doped sample. The thermal stability of films were also investigated. Un-doped Fe–N films deposited at 10% nitrogen partial pressure possess poor thermal stability. Doping of Al at 2 at.% improves it marginally, whereas, for 3, 6 and 12 at.% Al doping, it shows significant improvement. The obtained results have been explained in terms of thermodynamics of Fe–N and Al–N. - Highlights: • Doping effects of Al on Fe–N phase formation is studied. • Phase formation shows a non-monotonic behavior with Al doping. • Low doping levels of Al enhance and high levels retard the nitridation process. • Al doping beyond 3 at.% improve thermal stability of Fe–N films.

  13. Highly Efficient Catalytic Synthesis of α-Amino Acids under Phase-Transfer Conditions with a Novel Catalyst/Substrate Pair

    NARCIS (Netherlands)

    Belokon, Yuri N.; Kochetkov, Konstantin A.; Churkina, Tatiana D.; Ikonnikov, Nikolai S.; Larionov, Oleg V.; Harutyunyan, Syuzanna R.; Vyskočil, Štepán; North, Michael; Kagan, Henri B.

    2001-01-01

    A facile and fast enantioselective synthesis of α-amino acids with high ee values was achieved by the asymmetric alkylation of the glycine derivative under phase-transfer conditions with (R)- or (S)-2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN). The ee value of the catalyst can be as little as 40 %

  14. Mossbauer and magnetic study of solid phases formed by dissimilatory iron-reducing bacteria

    Czech Academy of Sciences Publication Activity Database

    Chistyakova, N.I.; Rusakov, V.S.; Shapkin, A.A.; Pigalev, P.A.; Kazakov, A.P.; Zhilina, T.N.; Zavarzina, D.G.; Lančok, Adriana; Kohout, J.; Greneche, J. M.

    2012-01-01

    Roč. 190, JUNE (2012), s. 721-724 ISSN 1012-0394 Institutional research plan: CEZ:AV0Z40320502 Keywords : Mossbauer spectroscopy * dissimilatory iron-reducing bacteria * iron oxides * biomagnetism Subject RIV: CA - Inorganic Chemistry

  15. In situ growth of capping-free magnetic iron oxide nanoparticles on liquid-phase exfoliated graphene

    NARCIS (Netherlands)

    Tsoufis, T.; Syrgiannis, Z.; Akhtar, N.; Prato, M.; Katsaros, F.; Sideratou, Z.; Kouloumpis, A.; Gournis, D.; Rudolf, P.

    2015-01-01

    We report a facile approach for the in situ synthesis of very small iron oxide nanoparticles on the surface of high-quality graphene sheets. Our synthetic strategy involved the direct, liquid-phase exfoliation of highly crystalline graphite (avoiding any oxidation treatment) and the subsequent

  16. Local probe investigations of the electronic phase diagrams of iron pnictides and chalcogenides

    Energy Technology Data Exchange (ETDEWEB)

    Materne, Philipp

    2015-09-24

    In this work, the electronic phase diagrams of Ca{sub 1-x}Na{sub x}Fe{sub 2}As{sub 2} and Fe{sub 1+y}Te were investigated using muon spin relaxation and Moessbauer spectroscopy. Single crystals of Ca{sub 1-x}Na{sub x}Fe{sub 2}As{sub 2} with x = 0.00, 0.35, 0.50, and 0.67 were examined. The undoped 122 parent compound CaFe{sub 2}As{sub 2} is a semi metal and shows antiferromagnetic commensurate spin density wave order below 167 K. By hole doping via Na substitution, the magnetic order is suppressed and superconductivity emerges including a Na-substitution level region, where both phases coexist. Upon Na substitution, a tilting of the magnetic moments out of the ab-plane is found. The interaction of the magnetic and superconducting order parameter in this coexistence region was studied and a nanoscopic coexistence of both order parameters is found. This is proven by a reduction of the magnetic order parameter of 7 % in x = 0.50 below the superconducting transition temperature. This reduction was analysed using Landau theory and a systematic correlation between the reduction of the magnetic order parameter and the ratio of the transition temperatures, T{sub c}/T{sub N}, for the 122 family of the iron pnictides is presented. The magnetic phase transition is accompanied by a tetragonal-to-orthorhombic phase transition. The lattice dynamics at temperatures above and below this magneto-structural phase transition were studied and no change in the lattice dynamics were found. However, the lattice for finite x is softer than for the undoped compound. For x = 0.67, diluted magnetic order is found. Therefore, the magnetism in Ca{sub 1-x}Na{sub x}Fe{sub 2}As{sub 2} is persistent even at optimal doping. The superconducting state is investigated by measuring the temperature dependence of the magnetic penetration depth, where two superconducting gaps with a weighting of nearly 50:50 are obtained. A temperature independent anisotropy of the magnetic penetration depth γ{sub

  17. Local probe investigations of the electronic phase diagrams of iron pnictides and chalcogenides

    International Nuclear Information System (INIS)

    Materne, Philipp

    2015-01-01

    In this work, the electronic phase diagrams of Ca 1-x Na x Fe 2 As 2 and Fe 1+y Te were investigated using muon spin relaxation and Moessbauer spectroscopy. Single crystals of Ca 1-x Na x Fe 2 As 2 with x = 0.00, 0.35, 0.50, and 0.67 were examined. The undoped 122 parent compound CaFe 2 As 2 is a semi metal and shows antiferromagnetic commensurate spin density wave order below 167 K. By hole doping via Na substitution, the magnetic order is suppressed and superconductivity emerges including a Na-substitution level region, where both phases coexist. Upon Na substitution, a tilting of the magnetic moments out of the ab-plane is found. The interaction of the magnetic and superconducting order parameter in this coexistence region was studied and a nanoscopic coexistence of both order parameters is found. This is proven by a reduction of the magnetic order parameter of 7 % in x = 0.50 below the superconducting transition temperature. This reduction was analysed using Landau theory and a systematic correlation between the reduction of the magnetic order parameter and the ratio of the transition temperatures, T c /T N , for the 122 family of the iron pnictides is presented. The magnetic phase transition is accompanied by a tetragonal-to-orthorhombic phase transition. The lattice dynamics at temperatures above and below this magneto-structural phase transition were studied and no change in the lattice dynamics were found. However, the lattice for finite x is softer than for the undoped compound. For x = 0.67, diluted magnetic order is found. Therefore, the magnetism in Ca 1-x Na x Fe 2 As 2 is persistent even at optimal doping. The superconducting state is investigated by measuring the temperature dependence of the magnetic penetration depth, where two superconducting gaps with a weighting of nearly 50:50 are obtained. A temperature independent anisotropy of the magnetic penetration depth γ λ = 1.5(4) is obtained, which is much smaller compared to other 122 compounds

  18. The kinetics of phase transformations of undercooled austenite of the Mn-Ni iron based model alloy

    OpenAIRE

    E. Rożniata; R. Dziurka; J. Pacyna

    2011-01-01

    Purpose: Present work corresponds to the research on the kinetics of phase transformations of undercooled austenite of Mn-Ni iron based model alloy. The kinetics of phase transformations of undercooled austenite of investigated alloy was presented on CCT diagram (continuous cooling transformation). Also the methodology of a dilatometric samples preparation and the method of the critical points determination were described.Design/methodology/approach: The austenitising temperature was defined ...

  19. Fenton-like oxidation of 2,4-DCP in aqueous solution using iron-based nanoparticles as the heterogeneous catalyst.

    Science.gov (United States)

    Li, Renchao; Gao, Ying; Jin, Xiaoying; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

    2015-01-15

    In this report, various iron-based nanoparticles (nZVI, n-Ni/Fe, n-Pd/Fe) were used for both heterogeneous Fenton oxidation of 2,4-dichlorophenol (2,4-DCP) and reductive dechlorination of 2,4-DCP in order to understand their roles in the Fenton oxidation and the reductive degradation of 2,4-DCP. The dechlorination efficiency of 2,4-DCP using nZVI, n-Ni/Fe, n-Fe/Pd and Fe(2)(+) was 6.48%, 6.80%, 15.95%, 5.02%, while Fenton oxidation efficiency of 2,4-DCP was 57.87%, 34.23%, 27.94%, 19.61% after 180 min, respectively. The new findings included a higher dechlorination using n-Fe/Pd due to Pd effective catalysis and the effective heterogeneous Fenton oxidation using nZVI depending on reductive dechlorination and heterogeneous Fenton oxidation occurs simultaneously. However, nZVI as the potential catalyst for heterogeneous Fenton was observed, and SEM, EDS and XRD demonstrate that change on the nZVI surface occurred due to the Fe(2+) leaching, and Total Organic Carbon (TOC) (30.71%) shows that 2,4-DCP was degraded. Furthermore, the experiment indicates that the pH values and concentration of 2,4-DCP significantly impacted on the heterogeneous Fenton oxidation of 2,4-DCP and the data fits well with the pseudo first-order kinetic model, which was a diffusion-controlled reaction. Finally, a possible mechanism for degradation of 2,4-DCP was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. 2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

    International Nuclear Information System (INIS)

    Blomberg, Sara; Gustafson, Johan; Lundgren, Edvin; Zhou, Jianfeng; Zetterberg, Johan

    2016-01-01

    In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

  1. Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

    Directory of Open Access Journals (Sweden)

    Carmen Nájera

    2004-04-01

    Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

  2. 2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

    Science.gov (United States)

    Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

    2016-11-01

    In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be

  3. Catalysts and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil

    2017-02-14

    The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

  4. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  5. Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers

    International Nuclear Information System (INIS)

    Stanley, Jacob; Boucheron, Leandra; Shpyrko, Oleg; Lin, Binhua; Meron, Mati

    2015-01-01

    Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles

  6. Homogeneous magnetic relaxation in iron-yttrium garnets in the vicinity of a phase transition

    International Nuclear Information System (INIS)

    Luzyanin, I.D.; Khavronin, V.P.

    1977-01-01

    Results are presented of an experimental investigation of the dynamics of homogeneous magnetization during a phase transition of the second kind in iron-yttrium garnet (IYG) single crystals of various shapes. It is shown that homogeneous relaxation significantly depends on both the magnitude of 4πchisub(st) (chisub(st) is static magnetic susceptibility) as well as on the relation between the variable field frequency (at which the investigation is carried out) and the characteristic energies. It is shown that beginning from temperatures such as 4πchisub(st) approximately 1, the characteristic dipole interaction energy becomes frequency dependent; this indicates that in this case Lorentz coupling between the dynamic susceptibility and homogeneous relaxation time is invalid. This is a principle point in investigations of homogeneous relaxation by radio-frequency techniques. The temperature dependence of the homogeneous relaxation time and static susceptibility is determined in the exchange region. It is found that the phase transition in IYG involves anomalous phenomena which manifest in release and absorption of heat by a sample and in the appearance of additional singularities in the temperature dependence of the homogeneous relaxation time

  7. Spontaneous phase separation during self-assembly in bi-dispersed spherical iron oxide nanoparticle monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Stanley, Jacob; Boucheron, Leandra; Shpyrko, Oleg, E-mail: lin@cars.uchicago.edu, E-mail: oshpyrko@physics.ucsd.edu [Department of Physics, University of California, San Diego, La Jolla, California 92093 (United States); Lin, Binhua, E-mail: lin@cars.uchicago.edu, E-mail: oshpyrko@physics.ucsd.edu; Meron, Mati [Center for Advanced Radiation Sources (CARS), University of Chicago, Chicago, Illinois 60637 (United States)

    2015-04-20

    Recent developments in the synthesis of iron oxide nanoparticles have resulted in the ability to fabricate roughly spherical particles with extremely high size uniformity (low polydispersity). These particles can form self-assembled monolayer films at an air-water interface. When the polydispersity of the particles is low, these monolayers can be well-ordered over a length scale dozens of times the particle size. The van der Waals force between the particles is what drives this self-assembly. Through the use of Grazing Incidence X-Ray Diffraction we demonstrate that, when these films are formed at the liquid surface from bi-dispersed solutions containing 10 and 20 nm spherical particles suspended in chloroform, the particles phase separate into well-ordered patches during the self-assembly process. Furthermore, the domain sizes of these phase separated regions are at most 2–3 times smaller than that of a film comprising only mono-dispersed particles and their degree of disorder is comparable. This is shown for multiple solutions with differing ratios of 10 and 20 nm particles.

  8. Phase composition of iron-rich R-Fe-Si (R=Dy, Ho, Er) alloys

    International Nuclear Information System (INIS)

    Ivanova, G.V.; Makarova, G.M.; Shcherbakova, E.V.; Belozerov, E.V.

    2005-01-01

    Phase composition is studied in iron-rich alloys of R-Fe-Si (R=Dy, Ho, Er). In the as-cast state R 2 (Fe, Si) 17 of type Th 2 Ni 17 and R(Fe, Si) 12 compounds are observed; in the alloys of rated composition of R(Fe 0.85 Si 0.15 ) 8.5 (R=Dy, Er) a compound R 2 (Fe, Si) 17 of Th 2 Zn 17 -type is revealed as well. The annealing at 1273 K results in formation of Dy 3 (Fe, Si) 29 and also the compounds with the presumed composition of Dy 4 (Fe, Si) 41 and Ho 4 (Fe, Si) 41 . As this takes place the alloys contain a transition structure as well that represents a set of small-sized areas with various type short-range order in mutual displacement of Fe-Fe(Si) dumpbell chains. The process of phase formation at 1273 K is faced with difficulties. Even the annealing for 1000 h does not result in the state of equilibrium [ru

  9. Easy solid-phase synthesis of pH-insensitive heterogeneous CNTs/FeS Fenton-like catalyst for the removal of antibiotics from aqueous solution.

    Science.gov (United States)

    Ma, Jie; Yang, Mingxuan; Yu, Fei; Chen, Junhong

    2015-04-15

    We report a facile solid method to synthesize efficient carbon-based Fenton-like catalyst (CNTs/FeS) using as-prepared carbon nanotubes (APCNTs), which makes full use of the iron nanoparticles in APCNTs without needless purification. Furthermore, the CNTs/FeS was characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric (TG) and other analysis techniques, and then the CNTs/FeS was used as a Fenton-like catalyst for removing ciprofloxacin from aqueous solution. Response Surface Methodology (RSM) was applied to find the effect of the reaction parameter and the optimum operating condition. Results shows the catalytic reaction had better suitability than previous studies in a wide range of pH values (pH 3-8) and the Fenton-like catalyst CNTs/FeS exhibits good catalytic activity for removing of antibiotic, which be attributed to the synergistic effect of adsorption-advanced oxidation and significantly improves efficiency of advanced oxidation. More importantly, the CNTs/FeS catalyst exhibit good regeneration performance and retains a high catalytic capacity (>75%) even after four reaction cycles. The catalytic mechanism were also studied further, the removal mechanism of ciprofloxacin by a CNTs/FeS heterogeneous Fenton-like process primarily involves three removal pathways occurring simultaneously: (a) adsorption removal by CNTs, (b) Fenton-like degradation catalyzed by FeS, (c) catalytic degradation by CNTs catalyst. And these actions also have synergistic effects for ciprofloxacin removal. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Synthesis of l-threitol-based crown ethers and their application as enantioselective phase transfer catalyst in Michael additions.

    Science.gov (United States)

    Rapi, Zsolt; Nemcsok, Tamás; Pálvölgyi, Ádám; Keglevich, György; Grün, Alajos; Bakó, Péter

    2017-06-01

    A few new l-threitol-based lariat ethers incorporating a monoaza-15-crown-5 unit were synthesized starting from diethyl l-tartrate. These macrocycles were used as phase transfer catalysts in asymmetric Michael addition reactions under mild conditions to afford the adducts in a few cases in good to excellent enantioselectivities. The addition of 2-nitropropane to trans-chalcone, and the reaction of diethyl acetamidomalonate with β-nitrostyrene resulted in the chiral Michael adducts in good enantioselectivities (90% and 95%, respectively). The substituents of chalcone had a significant impact on the yield and enantioselectivity in the reaction of diethyl acetoxymalonate. The highest enantiomeric excess (ee) values (99% ee) were measured in the case of 4-chloro- and 4-methoxychalcone. The phase transfer catalyzed cyclopropanation reaction of chalcone and benzylidene-malononitriles using diethyl bromomalonate as the nucleophile (MIRC reaction) was also developed. The corresponding chiral cyclopropane diesters were obtained in moderate to good (up to 99%) enantioselectivities in the presence of the threitol-based crown ethers. © 2017 Wiley Periodicals, Inc.

  11. Constituent phases and mechanical properties of iron oxide-additioned phosphoaluminate cement

    Directory of Open Access Journals (Sweden)

    Yang, Shuai

    2015-06-01

    Full Text Available Iron oxide was added to phosphoaluminate clinker and its effects on cement constituents were determined using XRD, DSC, SEM-EDS and conduction calorimetry analysis. The variations in compressive strength were also studied. The results showed that in moderate amounts, iron oxide acts as a mineraliser during clinker sintering, furthering the conversion of CA1-Y(PY to LHss at a lower temperature than normally required for that reaction. The main constituents of iron oxide-rich phosphoaluminate clinker included LHss, CA1-Y(PY, CP1-Z(AZ and ferrite. The EDS findings showed that the composition of the ferrite phase was nonuniform. The conclusion drawn was that by modifying the dose of Fe2O3 , the composition of phosphoaluminate cement can be controlled to produce clinker and cement compliant with different mechanical strength requirements. The conduction calorimetry findings were consistent with those results.Este trabajo estudia, mediante DRX DSC, SEM-EDS y calorimetría de conducción, el efecto de la adición de óxido de hierro a un clinker de fosfoaluminato, así como las variaciones sufridas en su resistencia a compresión. Los resultados mostraron que en cantidades moderadas, el óxido de hierro actúa como mineralizador durante la sinterización del clinker, promoviendo la conversión de CA1-Y(PY a LHss a una temperatura más baja de la normalmente requerida. Los componentes principales del clínker de fosfoaluminato con óxido de hierrop son LHss, CA1-Y(PY, CP1-Z(AZ y fase ferritica. Los resultados de EDS mostraron que la composición de esta fase ferrítica no era uniforme. DE este estudio se ha podido concluir que variando la dosificación del Fe2O3 , se puede controlar la composición del fosfoaluminato para producir clinker y cemento compatibles con diferentes requisitos de resistencia mecánica. Los resultados de calorimetría de conducción fueron consistentes con los resultados.

  12. 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.

  13. Catalyst dispersion and activity under conditions of temperature-staged liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  14. Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

    1993-02-01

    This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

  15. Phase diagram of (Li(1-x)Fe(x))OHFeSe: a bridge between iron selenide and arsenide superconductors.

    Science.gov (United States)

    Dong, Xiaoli; Zhou, Huaxue; Yang, Huaixin; Yuan, Jie; Jin, Kui; Zhou, Fang; Yuan, Dongna; Wei, Linlin; Li, Jianqi; Wang, Xinqiang; Zhang, Guangming; Zhao, Zhongxian

    2015-01-14

    Previous experimental results have shown important differences between iron selenide and arsenide superconductors which seem to suggest that the high-temperature superconductivity in these two subgroups of iron-based families may arise from different electronic ground states. Here we report the complete phase diagram of a newly synthesized superconducting (SC) system, (Li1-xFex)OHFeSe, with a structure similar to that of FeAs-based superconductors. In the non-SC samples, an antiferromagnetic (AFM) spin-density-wave (SDW) transition occurs at ∼127 K. This is the first example to demonstrate such an SDW phase in an FeSe-based superconductor system. Transmission electron microscopy shows that a well-known √5×√5 iron vacancy ordered state, resulting in an AFM order at ∼500 K in AyFe2-xSe2 (A = metal ions) superconductor systems, is absent in both non-SC and SC samples, but a unique superstructure with a modulation wave vector q = (1)/2(1,1,0), identical to that seen in the SC phase of KyFe2-xSe2, is dominant in the optimal SC sample (with an SC transition temperature Tc = 40 K). Hence, we conclude that the high-Tc superconductivity in (Li1-xFex)OHFeSe stems from the similarly weak AFM fluctuations as FeAs-based superconductors, suggesting a universal physical picture for both iron selenide and arsenide superconductors.

  16. Microemulsion and Sol-Gel Synthesized ZrO2-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural

    Directory of Open Access Journals (Sweden)

    Almudena Parejas

    2017-12-01

    Full Text Available Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively. Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO2 (especially Zr-SG are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

  17. Microemulsion and Sol-Gel Synthesized ZrO₂-MgO Catalysts for the Liquid-Phase Dehydration of Xylose to Furfural.

    Science.gov (United States)

    Parejas, Almudena; Montes, Vicente; Hidalgo-Carrillo, Jesús; Sánchez-López, Elena; Marinas, Alberto; Urbano, Francisco J

    2017-12-18

    Two series of catalysts were prepared by sol-gel and microemulsion synthetic procedure (SG and ME, respectively). Each series includes both pure Mg and Zr solids as well as Mg-Zr mixed solids with 25%, 50% and 75% nominal Zr content. The whole set of catalysts was characterized from thermal, structural and surface chemical points of view and subsequently applied to the liquid-phase xylose dehydration to furfural. Reactions were carried out in either a high-pressure autoclave or in an atmospheric pressure multi-reactor under a biphasic (organic/water) reaction mixture. Butan-2-ol and toluene were essayed as organic solvents. Catalysts prepared by microemulsion retained part of the surfactant used in the synthetic procedure, mainly associated with the Zr part of the solid. The MgZr-SG solid presented the highest surface acidity while the Mg3Zr-SG one exhibited the highest surface basicity among mixed systems. Xylose dehydration in the high-pressure system and with toluene/water solvent mixture led to the highest furfural yield. Moreover, the yield of furfural increases with the Zr content of the catalyst. Therefore, the catalysts constituted of pure ZrO₂ (especially Zr-SG) are the most suitable to carry out the process under study although MgZr mixed solids could be also suitable for overall processes with additional reaction steps.

  18. Effect of grain boundaries on shock-induced phase transformation in iron bicrystals

    Science.gov (United States)

    Zhang, Xueyang; Wang, Kun; Zhu, Wenjun; Chen, Jun; Cai, Mengqiu; Xiao, Shifang; Deng, Huiqiu; Hu, Wangyu

    2018-01-01

    Non-equilibrium molecular-dynamic simulations with a modified analytic embedded-atom model potential have been performed to investigate the effect of three kinds of grain boundaries (GBs) on the martensitic transformation in iron bicrystals with three different GBs under shock loadings. Our results show that the phase transition was influenced by the GBs. All three GBs provide a nucleation site for the α → ɛ transformation in samples shock-loaded with up = 0.5 km/s, and in particular, the elastic wave can induce the phase transformation at Σ3 ⟨110⟩ twist GB, which indicates that the phase transformation can occur at Σ3 ⟨110⟩ twist GB with a much lower pressure. The effect of GBs on the stress assisted transformation (SAT) mechanisms is discussed. All variants nucleating at the vicinity of these GBs meet the maximum strain work (MSW) criterion. Moreover, all of the variants with the MSW nucleate at Σ5 ⟨001⟩ twist GB and Σ3 ⟨110⟩ tilt GB, but only part of them nucleate at Σ3 ⟨110⟩ twist GB. This is because the coincident planes between both sides of the GB would affect the slip process, which is the second stage of the martensitic transformation and influences the selection of variant. We also find that the martensitic transformation at the front end of the bicrystals would give rise to stress attenuation in samples shock-loaded with up = 0.6 km/s, which makes the GBs seem to be unfavorable to the martensitic transformation. Our findings have the potential to affect the interface engineering and material design under high pressure conditions.

  19. Magnetic catalyst bodies

    NARCIS (Netherlands)

    Teunissen, Wendy; Bol, A.A.; Geus, John W.

    1999-01-01

    After a discussion about the importance of the size of the catalyst bodies with reactions in the liquid-phase with a suspended catalyst, the possibilities of magnetic separation are dealt with. Deficiencies of the usual ferromagnetic particles are the reactivity and the clustering of the

  20. Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

    Energy Technology Data Exchange (ETDEWEB)

    Zou, Chenyu; van Duin, Adri C.T.; Sorescu, Dan C.

    2012-06-01

    We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer–Tropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H{sub 2} and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.

  1. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  2. Aqueous dispersion of monodisperse magnetic iron oxide nanocrystals through phase transfer

    International Nuclear Information System (INIS)

    Yu, William W; Chang, Emmanuel; Sayes, Christie M; Drezek, Rebekah; Colvin, Vicki L

    2006-01-01

    A facile method was developed for completely transferring high quality monodisperse iron oxide nanocrystals from organic solvents to water. The as-prepared aqueous dispersions of iron oxide nanocrystals were extremely stable and could be functionalized for bioconjugation with biomolecules. These iron oxide nanocrystals showed negligible cytotoxicity to human breast cancer cells (SK-BR-3) and human dermal fibroblast cells. This method is general and versatile for many organic solvent-synthesized nanoparticles, including fluorescent semiconductor nanocrystals

  3. Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

    Science.gov (United States)

    Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

    2018-03-25

    Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

  4. Theoretical study of orbital ordering induced structural phase transition in iron pnictides

    Energy Technology Data Exchange (ETDEWEB)

    Jena, Sushree Sangita, E-mail: sushree@iopb.res.in; Rout, G. C., E-mail: gcr@iopb.res.in [Physics Enclave, Plot No-664/4825, Lane-4A, Shree Vihar, Bhubaneswar-24, Odisha (India); Panda, S. K., E-mail: skp@iopb.res.in

    2016-05-06

    We attribute the structural phase transition (SPT) in the parent compounds of the iron pnictides to orbital ordering. Due to anisotropy of the d{sub xz} and d{sub yz} orbitals in the xy plane, orbital ordering makes the orthorhombic structure more favorable and thus inducing the SPT. We consider a one band model Hamiltonian consisting of first and second-nearest-neighbor hopping of the electrons. We introduce Jahn-Tellar (JT) distortion in the system arising due to the orbital ordering present in this system. We calculate the electron Green’s function by using Zuvareb’s Green’s function technique and hence calculate an expression for the temperature dependent lattice strain which is computed numerically and self-consistently. The temperature dependent electron specific heat is calculated by minimizing the free energy of the system. The lattice strain is studied by varying the JT coupling and elastic constant of the system. The structural anomaly is studied through the electron occupation number and the specific heat by varying the physical parameters like JT coupling, lattice constant, chemical potential and hopping integrals of the system.

  5. Cooperative properties of single phases of complex oxide catalyst for oxidation of propylene to acrolein

    International Nuclear Information System (INIS)

    Orel, L.I.; Udalova, O.V.; Korchak, V.N.; Isaev, O.V.; Krylov, O.V.; Gershenzon, Yu.M.; Aptekar', E.L.

    1992-01-01

    Synergetic effect of increase of acrolein yield during propylene oxidation on mechanical mixture of (α + β)CoMoO 4 and MoO 3 , as well as CO and CO 2 yield on mixture of CoMoO 4 and Bi 2 O 3 ·2MoO 3 was revealed. It is shown that CoMoO 4 generates allyl radicals, desorption of these radicals to gaseous phase is not practically observed with MoO 3 , bismuth molybdates and Fe 2 O 3 · Fe 2 O 3 ·3MoO 3

  6. Influence of particle size and mineral phase in the analysis of iron ore slurries by Laser-Induced Breakdown Spectroscopy

    International Nuclear Information System (INIS)

    Michaud, Daniel; Leclerc, Remi; Proulx, Eric

    2007-01-01

    Laser-Induced Breakdown Spectroscopy (LIBS) was applied to the analysis of iron ore concentrates. The objective was to determine the influence of particle size and mineral phase on the LIBS signal. The LIBS spectra of hematite and magnetite ore concentrates were qualitatively indistinguishable from each other but magnetite yielded systematically less than hematite. This behavior could be set into an empirical equation to correct the iron peak intensities according to the level of magnetite in the analyzed sample. Similarly, an increase of the LIBS signal was observed as the particle size of the ore samples decreased. Again, an equation could be written down to correct the intensity of either iron or silicon in response to a variation of the average particle size of the ore concentrate. Using these corrections, proper response of the silicon signal against the concentration of silica in the samples was restored. The observed dependence of the strength of the iron signal upon the mineral phase is attributed to oxidation of magnetite into hematite

  7. 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....

  8. Phase purity of NiCo2O4, a catalyst candidate for electrolysis of water

    Science.gov (United States)

    Singer, J.; Fielder, W. L.; Garlick, R. G.; Negas, T.

    1987-01-01

    NiCo2O4 is shown to be difficult to obtain as a pure phase, and may never have been so obtained. High resolution x-ray diffractometry is required for its precise characterization. Film XRD is not likely to show the asymmetry in the spinel diffraction lines, caused by poorly crystallized NiO, as seen in diffractometer traces. The Co3O4 which is expected to accompany NiO as an impurity in NiCo2O4 syntheses has the same diffraction pattern as the binary oxide. Firings of the co-precipitated hydroxides at 300, 350, and 400 C, including one in pure O2, failed to produce single phase cobaltate. Scanning electron microscopy showed all the sintered products to range over several orders of magnitude in agglomerate/particle size. Surface areas by BET were all in the range 40 to 110 m sq/g, equivalent to particles of 200 to 100 Angstrom diameter. The spinel diffraction line breadths were compatible with those approximate dimensions.

  9. 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...

  10. CATALYTIC PERFORMANCES OF Fe2O3/TS-1 CATALYST IN PHENOL HYDROXYLATION REACTION

    Directory of Open Access Journals (Sweden)

    Didik Prasetyoko

    2010-07-01

    Full Text Available Hydroxylation reaction of phenol into diphenol, such as hydroquinone and catechol, has a great role in many industrial applications. Phenol hydroxylation reaction can be carried out using Titanium Silicalite-1 (TS-1 as catalyst and H2O2 as an oxidant. TS-1 catalyst shows high activity and selectivity for phenol hydroxylation reaction. However, its hydrophobic sites lead to slow H2O2 adsorption toward the active site of TS-1. Consequently, the reaction rate of phenol hydroxylation reaction is tends to be low. Addition of metal oxide Fe2O3 enhanced hydrophilicity of TS-1 catalyst. Liquid phase catalytic phenol hydroxylation using hydrogen peroxide as oxidant was carried out over iron (III oxide-modified TS-1 catalyst (Fe2O3/TS-1, that were prepared by impregnation method using iron (III nitrate as precursor and characterized by X-ray diffraction, infrared spectroscopy, nitrogen adsorption, pyridine adsorption, and hydrophilicity techniques. Catalysts 1Fe2O3/TS-1 showed maximum catalytic activity of hydroquinone product. In this research, the increase of hydroquinone formation rate is due to the higher hydrophilicity of Fe2O3/TS-1 catalysts compare to the parent catalyst, TS-1.   Keywords: Fe2O3/TS-1, hydrophilic site, phenol hydroxylation

  11. Optimisation of hydrogenation reactors with heterogeneous catalysts operated in trickle phase

    Energy Technology Data Exchange (ETDEWEB)

    Knoche, M. [CRI KataLeuna GmbH, Leuna (Germany)

    2010-12-30

    Maldistribution in trickle phase reactors is to be blamed for hot spot formation and non-ideal reaction. For a simple and quick evaluation, a virtually divided reactor model is presented for a better understanding and analysis of the consequences of liquid maldistribution. Based on this modelization, different methods are described to resolve microscopic and macroscopic maldistribution. The same model provides information to produce guidelines for reactor loading and evaluating the uneven effects of coking. It is shown that areas with specifically high liquid loads may suffer from insufficient gas supply and might therewith prevent a proper stoechiometric conversion of the gas with the liquid. In areas with lower liquid load, the gas has less hydraulic resistance and bypasses the effective reaction zone. (orig.)

  12. In vivo assessment of iron content of the cerebral cortex in healthy aging using 7-Tesla T2*-weighted phase imaging.

    Science.gov (United States)

    Buijs, Mathijs; Doan, Nhat Trung; van Rooden, Sanneke; Versluis, Maarten J; van Lew, Baldur; Milles, Julien; van der Grond, Jeroen; van Buchem, Mark A

    2017-05-01

    Accumulation of brain iron has been suggested as a biomarker of neurodegeneration. Increased iron has been seen in the cerebral cortex in postmortem studies of neurodegenerative diseases and healthy aging. Until recently, the diminutive thickness of the cortex and its relatively low iron content have hampered in vivo study of cortical iron accumulation. Using phase images of a T2*-weighted sequence at ultrahigh field strength (7 Tesla), we examined the iron content of 22 cortical regions in 70 healthy subjects aged 22-80 years. The cortex was automatically segmented and parcellated, and phase shift was analyzed using an in-house developed method. We found a significant increase in phase shift with age in 20 of 22 cortical regions, concurrent with current understanding of cortical iron accumulation. Our findings suggest that increased cortical iron content can be assessed in healthy aging in vivo. The high spatial resolution and sensitivity to iron of our method make it a potentially useful tool for studying cortical iron accumulation in healthy aging and neurodegenerative diseases. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Iron-Air Rechargeable Battery

    Science.gov (United States)

    Narayan, Sri R. (Inventor); Prakash, G.K. Surya (Inventor); Kindler, Andrew (Inventor)

    2014-01-01

    Embodiments include an iron-air rechargeable battery having a composite electrode including an iron electrode and a hydrogen electrode integrated therewith. An air electrode is spaced from the iron electrode and an electrolyte is provided in contact with the air electrode and the iron electrodes. Various additives and catalysts are disclosed with respect to the iron electrode, air electrode, and electrolyte for increasing battery efficiency and cycle life.

  14. Current limiting behavior in three-phase transformer-type SFCLs using an iron core according to variety of fault

    Science.gov (United States)

    Cho, Yong-Sun; Jung, Byung-Ik; Ha, Kyoung-Hun; Choi, Soo-Geun; Park, Hyoung-Min; Choi, Hyo-Sang

    To apply the superconducting fault current limiter (SFCL) to the power system, the reliability of the fault-current-limiting operation must be ensured in diverse fault conditions. The SFCL must also be linked to the operation of the high-speed recloser in the power system. In this study, a three-phase transformer-type SFCL, which has a neutral line to improve the simultaneous quench characteristics of superconducting elements, was manufactured to analyze the fault-current-limiting characteristic according to the single, double, and triple line-to-ground faults. The transformer-type SFCL, wherein three-phase windings are connected to one iron core, reduced the burden on the superconducting element as the superconducting element on the sound phase was also quenched in the case of the single line-to-ground fault. In the case of double or triple line-to-ground faults, the flux from the faulted phase winding was interlinked with other faulted or sound phase windings, and the fault-current-limiting rate decreased because the windings of three phases were inductively connected by one iron core.

  15. Effect of K promoter on the structure and catalytic behavior of supported iron-based catalysts in fischer-tropsch synthesis

    Directory of Open Access Journals (Sweden)

    F. E. M Farias

    2011-09-01

    Full Text Available Effects of K addition on the performance of supported Fe catalysts for Fischer - Tropsch synthesis (FTS were studied in a slurry reactor at 240 to 270ºC, 2.0 to 4.0 MPa and syngas H2/CO = 1.0. The catalysts were characterized by N2 adsorption, H2 temperature programmed reduction, X - ray diffraction, X - ray fluorescence, thermogravimetric analysis, scanning electron microscopy and dispersive X - ray spectroscopy. A strong interaction was observed between Fe and K, which inhibited the reduction of Fe catalyst. Addition of potassium increased the production of heavy hydrocarbons (C20+.

  16. Redox?Reversible Iron Orthovanadate Cathode for Solid Oxide Steam Electrolyzer

    OpenAIRE

    Gan, Lizhen; Ye, Lingting; Ruan, Cong; Chen, Shigang; Xie, Kui

    2015-01-01

    A redox?reversible iron orthovanadate cathode is demonstrated for a solid oxide electrolyser with up to 100% current efficiency for steam electrolysis. The iron catalyst is grown on spinel?type electronic conductor FeV2O4 by in situ tailoring the reversible phase change of FeVO4 to Fe+FeV2O4 in a reducing atmosphere. Promising electrode performances have been obtained for a solid oxide steam electrolyser based on this composite cathode.

  17. Gas-phase complexes formed between amidoxime ligands and vanadium or iron investigated using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Mustapha, Adetayo M; Pasilis, Sofie P

    2016-08-15

    Amidoxime-functionalized sorbents can be used to extract uranium from seawater. Iron(III) and vanadium(V) may compete with uranium for adsorption sites. We use 2,6-dihydroxyiminopiperidine (DHIP) and N(1) ,N(5) -dihydroxypentanediimidamide (DHPD) to model amidoxime functional groups and characterize the vanadium(V) and iron(III) complexes with these ligands. We also examine the effect of iron(III) and vanadium(V) on uranyl(VI) complexation by DHIP and DHPD. The experiments were carried out in positive ion mode using a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The effect on the mass spectra of changes in ligand, metal:ligand mole ratio, and pH was examined. Iron(III) formed a 1:2 metal:ligand complex with DHIP at all metal:ligand mole ratios and pH values investigated; it formed both 1:2 and 1:3 metal:ligand complexes with DHPD. Vanadium(V) formed 1:1 and 1:2 metal:ligand complexes with DHIP. A 1:2 metal:ligand complex was formed with DHPD at all vanadium(V):DHPD mole ratios investigated. Changes in solution pH did not affect the ions observed. The relative binding affinities of the metal ions towards DHIP followed the order iron(III) > vanadium(V) > uranyl(VI). This study presents a first look at the gas-phase vanadium(V)- and iron(III)-DHIP and -DHPD complexes using electrospray ionization mass spectrometry. These metals form stronger complexes with amidoxime ligands than uranyl(VI), and will affect uranyl(VI) adsorption to amidoxime-based sorbents. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  18. Removal of gas phase low-concentration toluene over Mn, Ag and Ce modified HZSM-5 catalysts by periodical operation of adsorption and non-thermal plasma regeneration.

    Science.gov (United States)

    Wang, Wenzheng; Wang, Honglei; Zhu, Tianle; Fan, Xing

    2015-07-15

    Ag/HZSM-5, Mn/HZSM-5, Ce/HZSM-5, Ag-Mn/HZSM-5 and Ce-Mn/HZSM-5 were prepared by impregnation method. Both their adsorption capacity and catalytic activity were investigated for the removal of gas phase low-concentration toluene by periodical operation of adsorption and non-thermal plasma regeneration. Results show that catalysts loaded with Ag (Ag/HZSM-5 and Ag-Mn/HZSM-5) had larger adsorption capacity for toluene than the other catalysts. And Ag-Mn/HZSM-5 displayed the best catalytic performance for both toluene oxidation by non-thermal plasma and byproducts suppression. On the other hand, the deactivated catalyst can be fully regenerated by calcining in air stream when its adsorption capacity and catalytic activity of the Ag-Mn/HZSM-5 catalyst was found to be decreased after 10 cycles of periodical adsorption and non-thermal regeneration. Copyright © 2015. Published by Elsevier B.V.

  19. Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts.

    Science.gov (United States)

    Jiménez-Gómez, Carmen Pilar; Cecilia, Juan A; Moreno-Tost, Ramón; Maireles-Torres, Pedro

    2017-04-10

    Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO 2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H 2 /FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h -1 . After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. An investigation of the physical and chemical changes occuring in a Fischer-Tropsch fixed bed catalyst during hydrocarbon synthesis

    International Nuclear Information System (INIS)

    Duvenhage, D.J.

    1990-01-01

    Deactivation studies: making use of fixed bed reactors, wet chemical analysis, surface area, pore volume determinations and X-ray diffraction spectrometry, scanning electron microscope spectrometry and secondary ion mass spectrometry techniques; were performed on a low temperature iron Fischer-Tropsch catalyst. It was revealed that this catalyst is mainly deactivated by sulphur poisoning, oxidation of the catalytic reactive phases, sintering of the iron crystallites and to a lesser extent deactivation through fouling of the catalytic surface by carbonaceous deposits. It was found that the top entry section of the catalyst bed deactivated relatively fast, the bottom exit section also deactivated, but not as fast as the top section. The central portion of the catalyst bed was least affected. Sulphur contaminants in the feed gas, even though present in only minute quantities, results in a loss of catalyst performance of the top section of the catalyst bed, while water, produced as a product from the Fischer-Tropsch reaction, oxidized and sintered the catalyst over the bottom section of the catalyst bed. 88 figs., 7 tabs., 224 refs

  1. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory; Laveille, Paco; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

    2015-01-01

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  2. Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

    KAUST Repository

    Biausque, Gregory

    2015-04-28

    Methods to synthesize NiPt bimetallic nanoparticles by a reversed-phase microemulsion, deposition of NiPt bimetallic nanoparticles on a support, and application of the supported catalyst for CO.sub.2 reforming of methane

  3. Effect of phase interaction on catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Chai, Shujing [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); The Institute of Seawater Desalination and Miltipurpose Utilization, State Oceanic Administration, Tianjin 300192 (China); Bai, Xueqin; Li, Jing; Liu, Cheng; Ding, Tong; Tian, Ye; Liu, Chang [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China); Xian, Hui [Tianjin Polytechnic University, School of Computer Science & Software Engineering, Tianjin 300387 (China); Mi, Wenbo [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparation Technology, Faculty of Science, Tianjin University, Tianjin 300354 (China); Li, Xingang, E-mail: xingang_li@tju.edu.cn [Collaborative Innovation Center of Chemical Science & Engineering (Tianjin), Tianjin Key Laboratory of Applied Catalysis Science & Technology, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354 (China)

    2017-04-30

    Highlights: • Activity for CO oxidation is greatly enhanced by interaction between SnO{sub 2} and Al{sub 2}O{sub 3}. • Interaction between SnO{sub 2} and Al{sub 2}O{sub 3} phases can generate oxygen vacancies. • Oxygen vacancies play an import role for catalytic CO oxidation. • Sn{sup 4+} cations are the effective sites for catalytic CO oxidation. • Langmuir-Hinshelwood model is preferred for catalytic CO oxidation. - Abstract: We investigated the catalytic CO oxidation over the SnO{sub 2}/Al{sub 2}O{sub 3} model catalysts. Our results show that interaction between the Al{sub 2}O{sub 3} and SnO{sub 2} phases results in the significantly improved catalytic activity because of the formation of the oxygen vacancies. The oxygen storage capacity of the SnO{sub 2}/Al{sub 2}O{sub 3} catalyst prepared by the physically mixed method is nearly two times higher than that of the SnO{sub 2}, which probably results from the change of electron concentration on the interface of the SnO{sub 2} and Al{sub 2}O{sub 3} phases. Introducing water vapor to the feeding gas would a little decrease the activity of the catalysts, but the reaction rate could completely recover after removal of water vapor. The kinetics results suggest that the surface Sn{sup 4+} cations are effective CO adsorptive sites, and the surface adsorbed oxygen plays an important role upon CO oxidation. The reaction pathways upon the SnO{sub 2}-based catalysts for CO oxidation follow the Langmuir-Hinshelwood model.

  4. 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.

  5. SCR at bio fuels combustion - phase 2. Measures to extend catalyst life time; SCR vid biobraensleeldning - etapp 2. Aatgaerder foer att foerlaenga katalysatorns livslaengd

    Energy Technology Data Exchange (ETDEWEB)

    Andersson, Christer; Bodin, Henrik; Sahlqvist, Aasa [Vattenfall Utveckling AB, Aelvkarleby (Sweden); Khodayari, Raziyeh; Odenbrand, Ingemar [Lund Univ. (Sweden). Dept. of Chemical Engineering II

    2000-07-01

    In this project phase, the deactivation of catalysts during combustion of bio fuels, and different methods of regeneration have been investigated. The overall purpose is to improve the economic and technical possibilities to use SCR at bio fuels combustion. The two different methods for regeneration are washing with water and so called sulphation (treatment with sulphur dioxide). The results from wood fired FB-boilers show that the catalyst lose 25% (average) of the relative activity during a normal heat production season. The tendency is that a boiler with short residence time between final combustion and catalyst and/or high flame temperatures gives a faster deactivation. Such unfavourable conditions arise in FB-boilers with a large part of the combustion in freeboard/cyclone. The alkali content of the fuel (wood fuel) is of minor importance for the deactivation rate compared with the combustion conditions. The flue gas temperature within the interval 250 - 375 deg C is not an important parameter for the deactivation in the time interval 3 000 - 6 000 h. The 'new' honeycomb catalysts that were tested during phase two, BiotypA-C, evidently show different deactivation trends. The highly active BiotypC e.g. increases its activity during the first thousand hours. Calculations indicate that BiotypC at 315 deg C requires the smallest volume of catalyst over ten years of operation in order to maintain given performance. Practical consequences for downstream equipment also need to be carefully checked. Sulphation with SO{sub 2} works in the laboratory as a regeneration method for all of the tested samples. The sulphatised samples deactivation are almost comparable to a fresh sample when exposed to flue gas. About 80 % of the lost activity can be regained only by using sulphation. Plate-type catalysts gets a somewhat lower increase in activity compared to honeycomb-types, probably related to chemical rather than geometric design. High SO{sub 2}-concentration

  6. Effect of shear strain on the α-ε phase transition of iron: a new approach in the rotational diamond anvil cell

    International Nuclear Information System (INIS)

    Ma Yanzhang; Selvi, Emre; Levitas, Valery I; Hashemi, Javad

    2006-01-01

    The effect of shear strain on the iron α-ε phase transformation has been studied using a rotational diamond anvil cell (RDAC). The initial transition is observed to take place at the reduced pressure of 10.8 GPa under pressure and shear operation. Complete phase transformation was observed at 15.4 GPa. The rotation of an anvil causes limited pressure elevation and makes the pressure distribution symmetric in the sample chamber before the phase transition. However, it causes a significant pressure increase at the centre of the sample and brings about a large pressure gradient during the phase transformation. The resistance to the phase interface motion is enhanced due to strain hardening during the pressure and shear operations on iron and this further increases the transition pressure. The work of macroscopic shear stress and the work of the pressure and shear stress at the defect tips account for the pressure reduction of the iron phase transition

  7. Water-dispersable hybrid Au-Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki-Miyaura and Heck reactions

    KAUST Repository

    Song, Hyon Min

    2012-01-01

    The catalytic activities of water-dispersable Au@Pd core-shell nanoparticles (NPs) and Au-Pd alloy NPs were examined. There is growing interest in Au-Pd hybridized NPs in a supported matrix or non-supported forms as catalysts in various reactions that are not limited to conventional Pd-related reactions. Four different Au@Pd core-shell NPs in this study were prepared at room temperature with help from the emulsion phase surrounding the Au core NPs. Au-Pd alloy NPs were prepared over 90 °C, and underwent phase transfer to aqueous medium for their catalytic use. Au@Pd core-shell NPs show catalytic activity in ethanol oxidation reactions as electrocatalysts, and both core-shell and alloy NPs are good to excellent catalysts in various Suzuki-Miyaura and Heck reactions as heterogeneous catalysts. Specifically, Au@Pd core-shell NPs with sharp branched arms show the highest yield in the reactions tested in this study. A relatively small amount (0.25 mol%) was used throughout the catalytic reactions. © 2012 The Royal Society of Chemistry.

  8. Atomic scale insights into electrochemical versus gas phase oxidation of HCl over RuO2-based catalysts: A comparative review

    International Nuclear Information System (INIS)

    Over, Herbert

    2013-01-01

    In this article our current understanding of the electro-catalyzed chlorine evolution reaction (CER) in comparison with that of the heterogeneously-catalyzed gas phase oxidation of HCl (Deacon process: heterogeneous catalysis) over RuO 2 -based catalysts will be reviewed. Both types of harsh reactions are chemically similar: The main concern is catalyst stability, and in both cases the best catalyst contains RuO 2 as the catalytically active component so that a critical comparison may provide new insights into the underlying physicochemical processes. It is the primary scope of this review addresses atomic scale information on the RuO 2 -catalyzed HCl oxidation reaction either in electrochemical or in gas phase environment. In particular, the involved reaction mechanisms and the reason for the extraordinary stability of RuO 2 under such harsh reaction conditions will be discussed, emphasizing similarities and differences in the Deacon process and the CER and what can be learnt from this comparison. The distinct properties of RuO 2 , which are responsible for its extraordinary catalytic performance in both the CER and the Deacon process, are highlighted

  9. Mutagenicity of diesel engine exhaust is eliminated in the gas phase by an oxidation catalyst but only slightly reduced in the particle phase.

    Science.gov (United States)

    Westphal, Götz A; Krahl, Jürgen; Munack, Axel; Ruschel, Yvonne; Schröder, Olaf; Hallier, Ernst; Brüning, Thomas; Bünger, Jürgen

    2012-06-05

    Concerns about adverse health effects of diesel engine emissions prompted strong efforts to minimize this hazard, including exhaust treatment by diesel oxidation catalysts (DOC). The effectiveness of such measures is usually assessed by the analysis of the legally regulated exhaust components. In recent years additional analytical and toxicological tests were included in the test panel with the aim to fill possible analytical gaps, for example, mutagenic potency of polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nPAH). This investigation focuses on the effect of a DOC on health hazards from combustion of four different fuels: rapeseed methyl ester (RME), common mineral diesel fuel (DF), SHELL V-Power Diesel (V-Power), and ARAL Ultimate Diesel containing 5% RME (B5ULT). We applied the European Stationary Cycle (ESC) to a 6.4 L turbo-charged heavy load engine fulfilling the EURO III standard. The engine was operated with and without DOC. Besides regulated emissions we measured particle size and number distributions, determined the soluble and solid fractions of the particles and characterized the bacterial mutagenicity in the gas phase and the particles of the exhaust. The effectiveness of the DOC differed strongly in regard to the different exhaust constituents: Total hydrocarbons were reduced up to 90% and carbon monoxide up to 98%, whereas nitrogen oxides (NO(X)) remained almost unaffected. Total particle mass (TPM) was reduced by 50% with DOC in common petrol diesel fuel and by 30% in the other fuels. This effect was mainly due to a reduction of the soluble organic particle fraction. The DOC caused an increase of the water-soluble fraction in the exhaust of RME, V-Power, and B5ULT, as well as a pronounced increase of nitrate in all exhausts. A high proportion of ultrafine particles (10-30 nm) in RME exhaust could be ascribed to vaporizable particles. Mutagenicity of the exhaust was low compared to previous investigations. The DOC reduced

  10. Investigation of the promoting effect of Mn on a Pt/C catalyst for the steam and aqueous phase reforming of glycerol

    Energy Technology Data Exchange (ETDEWEB)

    Bossola, Filippo; Pereira-Hernández, Xavier Isidro; Evangelisti, Claudio; Wang, Yong; Dal Santo, Vladimiro

    2017-05-01

    The catalytic performances in steam reforming (SR) and aqueous phase reforming (APR) of glycerol of a bimetallic Pt-Mn catalyst supported on activated carbon are investigated and correlated with the surface properties of the catalyst. Under SR conditions, Mn showed a significant promoting effect over Pt/C, both in terms of hydrogen production rate and conversion, with a higher selectivity toward the glycerol dehydration products. Upon addition of Mn the amount of strong Lewis acid sites increased, promoting the dehydration of glycerol and favoring the CAO over CAC cleavage at expenses of hydrogen selectivity. Conversely, under APR conditions, a slightly higher hydrogen selectivity and only minimal enhancement in hydrogen production were found, while the products selectivity was comparable to Pt/C. Most of Mn leached into the aqueous media, but the remaining (<5% of the fresh parent sample) might be alloyed with Pt and promote the CO desorption from neighbor Pt sites.

  11. Methodology for determination of trace elements in mineral phases of iron banded formation by LA-ICP-MS

    International Nuclear Information System (INIS)

    Sousa, Denise V.M. de; Nalini Junior, Herminio A.; Sampaio, Geraldo M.S.; Abreu, Adriana T. de; Lana, Cristiano de C.

    2015-01-01

    The study of the chemical composition of mineral phases of iron formation (FF), especially of trace elements, is an important tool in the understanding of the genesis of these rocks and the contribution of the phases in the composition of whole rock. Low mass fraction of such elements in the mineral phases present in this rock type requires a suitable analytical procedure. The laser ablation technique coupled with ICP-MS (LA-ICP-MS) has been widely used for determination of trace elements in geological samples. Thus, the aim of this study is to develop calibration curves for determination of trace elements (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) in mineral phases of banded iron formations by LA-ICP-MS. Several certified reference materials (CRM) were used for calibrate the equipment. The analytical conditions were checked by CRM NIST SRM 614. The results were satisfactory, since the curves showed good linearity coefficients, good accuracy and precision of results. (author)

  12. Halloysite Nanotubes as a New Adsorbent for Solid Phase Extraction and Spectrophotometric Determination of Iron in Water and Food Samples

    Science.gov (United States)

    Samadi, A.; Amjadi, M.

    2016-07-01

    Halloysite nanotubes (HNTs) have been introduced as a new solid phase extraction adsorbent for preconcentration of iron(II) as a complex with 2,2-bipyridine. The cationic complex is effectively adsorbed on the sorbent in the pH range of 3.5-6.0 and efficiently desorbed by trichloroacetic acid. The eluted complex has a strong absorption around 520 nm, which was used for determination of Fe(II). After optimizing extraction conditions, the linear range of the calibration graph was 5.0-500 μg/L with a detection limit of 1.3 μg/L. The proposed method was successfully applied for the determination of trace iron in various water and food samples, and the accuracy was assessed through the recovery experiments and analysis of a certified reference material (NIST 1643e).

  13. CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

    Science.gov (United States)

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

    2014-07-01

    An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

  14. Effect of catalyst preparation on the yield of carbon nanotube growth

    International Nuclear Information System (INIS)

    Escobar, Mariano; Rubiolo, Gerardo; Candal, Roberto; Goyanes, Silvia

    2009-01-01

    Multi-wall carbon nanotubes (MWCNTs) were synthesized by catalytic chemical vapor deposition (CVD) on catalytic iron nanoparticles dispersed in a silica matrix, prepared by sol gel method. In this contribution, variation of gelation condition on catalyst structure and its influence on the yield of carbon nanotubes growth was studied. The precursor utilized were tetraethyl-orthosilicate and iron nitrate. The sols were dried at two different temperatures in air (25 or 80 deg. C) and then treated at 450 deg. C for 10 h. The xerogels were introduced into the chamber and reduced in a hydrogen/nitrogen (10%v/v) atmosphere at 600 deg. C. MWCNTs were formed by deposition of carbon atoms from decomposition of acetylene at 700 deg. C. The system gelled at RT shows a yield of 100% respect to initial catalyst mass whereas the yield of that gelled at 80 deg. C was lower than 10%. Different crystalline phases are observed for both catalysts in each step of the process. Moreover, TPR analysis shows that iron oxide can be efficiently reduced to metallic iron only in the system gelled at room temperature. Carbon nanotubes display a diameter of about 25-40 nm and several micron lengths. The growth mechanism of MWCNTs is base growth mode for both catalysts.

  15. Effect of catalyst preparation on the yield of carbon nanotube growth

    Energy Technology Data Exchange (ETDEWEB)

    Escobar, Mariano, E-mail: mescobar@df.uba.a [Dep. Quimica Inorganica, Analitica y Quimica Fisica, FCEyN, UBA, Ciudad Universitaria (1428), Bs As (Argentina); LP and MC, Dep. Fisica, FCEyN, UBA (Argentina); Rubiolo, Gerardo [Unidad de Actividad Materiales, CNEA, Av Gral Paz 1499, San Martin (1650), Bs As (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Candal, Roberto [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Instituto de Fisico-quimica de Materiales, Ambiente y Energia (INQUIMAE), CONICET - UBA (Argentina); Goyanes, Silvia [LP and MC, Dep. Fisica, FCEyN, UBA (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina)

    2009-10-01

    Multi-wall carbon nanotubes (MWCNTs) were synthesized by catalytic chemical vapor deposition (CVD) on catalytic iron nanoparticles dispersed in a silica matrix, prepared by sol gel method. In this contribution, variation of gelation condition on catalyst structure and its influence on the yield of carbon nanotubes growth was studied. The precursor utilized were tetraethyl-orthosilicate and iron nitrate. The sols were dried at two different temperatures in air (25 or 80 deg. C) and then treated at 450 deg. C for 10 h. The xerogels were introduced into the chamber and reduced in a hydrogen/nitrogen (10%v/v) atmosphere at 600 deg. C. MWCNTs were formed by deposition of carbon atoms from decomposition of acetylene at 700 deg. C. The system gelled at RT shows a yield of 100% respect to initial catalyst mass whereas the yield of that gelled at 80 deg. C was lower than 10%. Different crystalline phases are observed for both catalysts in each step of the process. Moreover, TPR analysis shows that iron oxide can be efficiently reduced to metallic iron only in the system gelled at room temperature. Carbon nanotubes display a diameter of about 25-40 nm and several micron lengths. The growth mechanism of MWCNTs is base growth mode for both catalysts.

  16. [Iron nutrition in Mapuche infants fed with human milk (2d phase)].

    Science.gov (United States)

    Franco, E; Hertrampf, E; Rodríguez, E; Illanes, J C; Palacios, L; Llaguno, S; Lettelier, A

    1990-01-01

    Blood hemoglobin, serum iron, total iron binding capacity (TIBC) and serum ferritin were measured in 140 healthy rural mapuche (southern Chile's indigenous ethnic group) infants aged 8 to 15 months: 90 had been exclusively breast fed for the first 5 or 6 months of life, then solid foods were introduced but cow's milk was never given to them. The remaining 50, which were all weaned at nearly 4 months of age and then given cow's milk and solid foods at the corresponding age, were designated as controls. Anemia was detected in 4.5% of breast fed infants and in 38% of controls. Evidence of iron deficient erythropoiesis was found in 5% and 81% of cases and controls, respectively. Human milk apparently protects this ethnic group from iron deficiency anemia and this protection seems to be better in mapuche infants than in other groups of chilean infants, because these late have shown 30% incidence of anemia around the first year of life in other studies. More studies on differences in iron nutritional state among mapuche and non mapuche are needed and are under way.

  17. Microwave plasma enhanced chemical vapor deposition growth of few-walled carbon nanotubes using catalyst derived from an iron-containing block copolymer precursor

    International Nuclear Information System (INIS)

    Wang Peng; Lu, Jennifer; Zhou, Otto

    2008-01-01

    The microwave plasma enhanced chemical vapor deposition (MPECVD) method is now commonly used for directional and conformal growth of carbon nanotubes (CNTs) on supporting substrates. One of the shortcomings of the current process is the lack of control of the diameter and diameter distribution of the CNTs due to difficulties in synthesizing well-dispersed catalysts. Recently, block copolymer derived catalysts have been developed which offer the potential of fine control of both the size of and the spacing between the metal clusters. In this paper we report the successful growth of CNTs with narrow diameter distribution using polystyrene-block-polyferrocenylethylmethylsilane (PS-b-PFEMS) as the catalyst precursor. The study shows that higher growth pressure leads to better CNT growth. Besides the pressure, the effects on the growth of CNTs of the growth parameters, such as temperature and precursor gas ratio, are also studied

  18. In-Situ Liquid Hydrogenation of m-Chloronitrobenzene over Fe-Modified Pt/Carbon Nanotubes Catalysts

    Directory of Open Access Journals (Sweden)

    Feng Li

    2018-02-01

    Full Text Available In-situ liquid-phase hydrogenation of m-chloronitrobenzene (m-CNB based on aqueous-phase reforming (APR of ethanol and catalytic hydrogenation was carried out over Fe-modified Pt/carbon nanotubes (CNTs catalysts. The effects of Pt loading over CNTs and Fe modification on the catalytic performance of Pt/CNTs catalysts were studied. In-tube loading of Pt particles, compared with out-tube loading, considerably improved the catalytic activity. With in-tube loading, Fe-modified Pt/CNTs catalysts further improved the m-CNB in-situ hydrogenation performance. After Fe modification, Pt–Fe/CNTs catalysts formed, inside CNTs, a Pt–Fe alloy and iron oxides, which both improved catalytic hydrogenation performance and significantly enhanced ethanol APR hydrogen producing performance, thereby increasing the m-CNB in-situ hydrogenation reactivity.

  19. Electronic Phase Separation in the Slightly Underdoped Iron Pnictide Superconductor Ba1-xKxFe2As2

    DEFF Research Database (Denmark)

    Park, J.T.; Inosov, D.S.; Niedermayer, C.

    2009-01-01

    Here we present a combined study of the slightly underdoped novel pnictide superconductor Ba1-xKxFe2As2 by means of x-ray powder diffraction, neutron scattering, muon-spin rotation (µSR), and magnetic force microscopy (MFM). Static antiferromagnetic order sets in below Tm70 K as inferred from......-state regions on a lateral scale of several tens of nanometers. Our findings indicate that such mesoscopic phase separation can be considered an intrinsic property of some iron pnictide superconductors....

  20. 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

  1. Session 6: Liquid-phase chloro-benzene hydrogenolysis over alkali-doped zirconia supported palladium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Aramendia, M.A.; Borau, V.; Jimenez, C.; Marinas, A.; Marinas, J.M.; Moreno, J.M.; Ruiz, J.R.; Urbano, F.J. [University of Cordoba. Marie Curie Building, Dept. of Organic Chemistry (Spain)

    2004-07-01

    Chlorinated hydrocarbons constitute one of the most important kind of organic pollutants due to their environmental impact and noxious effects. Catalytic hydro-dehalogenation is now emerging as a promising non-destructive alternative technology whereby the chlorinated waste is converted to products with a commercial value. It is simple, safe, effective, and it ensures, in many instances, the regeneration of the initial raw material. One of the main problems of catalytic hydro-dehalogenation arise from the deactivating effect of the hydrogen halide released as by product. This can be surpassed by, for example, adding a base, such as NaOH, or modification of the catalyst in order to neutralize the hydrogen halide released. In conclusion, the alkali modification of the zirconia supported catalysts did not enhance the catalytic activity in comparison to the undoped Pd/ZrO{sub 2}. Moreover, the lithium doped catalyst exhibits very poor results in initial rate and final chloro-benzene conversion. This could be related to the reduction in BET surface area caused by the doping together with a lower enhancement of the surface basicity of the doped catalysts. (authors)

  2. LIQUID PHASE SELECTIVE OXIDATION OF ETHYLBENZENE OVER ACTIVATED AL2O3 SUPPORTED V2O5 CATALYST

    Science.gov (United States)

    Acetophenone, a very useful industrial chemical for fragrance and flavoring agent and a solvent for plastics and resins, is usually produced as a byproduct of phenol production from cumeme. Aluminia supported vandium oxide catalyst is now explored for the selective oxidation of e...

  3. The effect of temperature on nascent morphology of polyethylene polymerized over solution-phase flat model catalysts

    NARCIS (Netherlands)

    Jiang, S.D.; Kong, B.L.; Han, W.; Thune, P.C.; Yang, X.Z.; Loos, J.; Yan, S.K.

    2009-01-01

    The structure and morphology of polyethylene (PE) produced during solution polymerization using bis(imino)pyridyl metal catalysts supported by flat SiO2/Si(100) wafers were investigated by atomic force microscopy (AFM) and electron diffraction. Depending on the polymerization temperature, ranging

  4. Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

    NARCIS (Netherlands)

    Mahfud, F. H.; Ghijsen, F.; Heeres, H. J.

    2007-01-01

    The use of homogeneous ruthenium catalysts to hydrogenate the water-soluble fraction of pyrolysis oil is reported. Pyrolysis oil, which is obtained by fast pyrolysis of lignocellulosic biomass at 450-600 degrees C, contains significant amounts of aldehydes and ketones (e.g. 1-hydroxy-2-propanone (1)

  5. exchanged Mg-Al hydrotalcite catalyst

    Indian Academy of Sciences (India)

    ) catalysts, ... The catalyst can be easily separated by simple filtration ... surface area by the single-point N2 adsorption method ... concentration of carbonate anions (by treating the cat- .... hydrotalcite phase along with copper hydroxide and.

  6. Phase III randomized trial comparing intravenous to oral iron in patients with cancer-related iron deficiency anemia not on erythropoiesis stimulating agents.

    Science.gov (United States)

    Noronha, Vanita; Joshi, Amit; Patil, Vijay Maruti; Banavali, Shripad D; Gupta, Sudeep; Parikh, Purvish M; Marfatia, Shalaka; Punatar, Sachin; More, Sucheta; Goud, Supriya; Nakti, Dipti; Prabhash, Kumar

    2018-04-01

    We aimed to find the optimal route of iron supplementation in patients with malignancy and iron deficiency (true or functional) anemia not receiving erythropoiesis stimulating agents (ESA). Adult patients with malignancy requiring chemotherapy, hemoglobin (Hb) 10% were randomized to intravenous (IV) iron sucrose or oral ferrous sulfate. The primary endpoint was change in Hb from baseline to 6 weeks. Secondary endpoints included blood transfusion, quality of life (QoL), toxicity, response and overall survival. A total of 192 patients were enrolled over 5 years: 98 on IV arm and 94 on oral arm. Median age was 51 years; over 95% patients had solid tumors. The mean absolute increase in Hb at 6 weeks was 0.11 g/dL (standard deviation [SD]: 1.48) in IV arm and -0.16 g/dL (SD: 1.36) in oral arm, P = 0.23. Twenty-three percent patients on IV iron and 18% patients on oral iron had a rise in Hb of ≥1 g/dL at 6 weeks, P = 0.45. Thirteen patients (13.3%) on the IV iron arm and 14 patients (14.9%) on the oral arm required blood transfusion, P = 1.0. Gastrointestinal toxicity (any grade) developed in 41% patients on IV iron and 44% patients on oral iron, P = 1.0. 5 patients on IV iron and none on oral iron had hypersensitivity, P = 0.06. QoL was not significantly different between the two arms. IV iron was not superior to oral iron in patients with malignancy on chemotherapy and iron deficiency anemia. © 2017 John Wiley & Sons Australia, Ltd.

  7. Vacancy enhanced formation and phase transition of Cu-rich precipitates in α - iron under neutron irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Lv, G. C. [Basic Experimental Center of Natural Science, University of Science and Technology Beijing, Beijing, 100083 (China); Corrosion and Protection Center, Key Laboratory of Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing, 100083 (China); Zhang, H. [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada, T6G2V4 (Canada); He, X. F.; Yang, W. [China Institute of Atomic Energy, Beijing, 102413 (China); Su, Y. J., E-mail: yjsu@ustb.edu.cn [Corrosion and Protection Center, Key Laboratory of Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing, 100083 (China)

    2016-04-15

    In this paper, we employed both molecular statics and molecular dynamics simulation methods to investigate the role of vacancies in the formation and phase transition of Cu-rich precipitates in α-iron. The results indicated that vacancies promoted the diffusion of Cu atoms to form Cu-rich precipitates. After Cu-rich precipitates formed, they further trapped vacancies. The supersaturated vacancy concentration in the Cu-rich precipitate induced a shear strain, which triggered the phase transition from bcc to fcc structure by transforming the initial bcc (110) plane into fcc (111) plane. In addition, the formation of the fcc-twin structure and the stacking fault structure in the Cu-rich precipitates was observed in dynamics simulations.

  8. Structural phase transitions in Iron - based superconductors BaFe2-xCrxAs2 under high pressure

    International Nuclear Information System (INIS)

    Uhoya, W.O.; Montgomery, J.M.; Samudrala, G.K.; Tsoi, G.M.; Vohra, Y.K.; Sefar, A.S.

    2011-01-01

    Pure BaFe 2 As 2 with the ThCr 2 Si 2 -type crystal structure under ambient conditions is known to superconduct under high pressure and undergo an isostructural phase transition from tetragonal to collapsed tetragonal phase which is accompanied by anomalous compressibility effects. Presently, there is no reported work on the crystal structure on any of the chemically doped 122- iron based superconductors under high pressure. We have carried out the electrical resistance measurements and high pressure X-ray diffraction studies on Chromium doped samples of BaFe 2-x Cr x As 2 (x = 0, 0.05, 0.15, 0.4, 0.61) to a pressure of 75 GPa and a temperature of 10K using a synchrotron source and designer diamond anvils, so as to investigate the influence of chemical doping and high pressure on crystal structure and superconductivity

  9. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids

    Czech Academy of Sciences Publication Activity Database

    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, Petra; Filip, Petr; Vesel, A.

    2011-01-01

    Roč. 387, 1-3 (2011), s. 99-103 ISSN 0927-7757 Grant - others:GA ČR(CZ) GD104/09/H080; OP VaVpI(XE) CZ.1.05/2.1.00/03.0111 Program:GD Institutional research plan: CEZ:AV0Z20600510 Keywords : carbonyl iron * magnetorheological fluid * plasma * viscoelasticity Subject RIV: BK - Fluid Dynamics Impact factor: 2.236, year: 2011

  10. Mineralogical investigations of the interaction between iron corrosion products and bentonite from the NF-PRO Experiments (Phase 1)

    Energy Technology Data Exchange (ETDEWEB)

    Milodowski, A.E.; Cave, M.R.; Kemp, S.J.; Taylor, B.H.; Vickers, B.P.; Green, K.A.; Williams, C.L.; Shaw, R.A. (British Geological Survey (United Kingdom))

    2009-01-15

    This report summarises the findings of a programme of work under taken by the British Geological Survey (BGS) on behalf of SKB, to characterise the mineralogical alteration of compacted bentonite from experiments designed to study the interaction between iron corrosion and bentonite. The experiments were undertaken by Serco Assurance (Culham Laboratory, Oxfordshire, United Kingdom), and were co-funded by SKB within the EU Framework 6 NF-PRO Project. Reacted bentonite residues from three NF-PRO Experiments - NFC12, NFC16 and NFC17 were examined by BGS using; X-ray diffraction analysis (XRD); petrographical analysis with backscattered scanning electron microscopy (BSEM) and energy-dispersive X-ray microanalysis (EDXA) techniques, cation exchange capacity (CEC) and exchangeable cation analysis; and sequential chemical extraction. Bentonite immediately adjacent to corroding steel was found to have interacted with Fe released from the corroding metal. This resulted in the formation of narrow haloes of altered bentonite around the corroding steel wires, in which the clay matrix was significantly enriched in Fe. Detailed petrographical observation found no evidence for the formation of discrete iron oxide or iron oxyhydroxide phases within the clay matrix but appeared to show that the clay particles themselves had become enriched in Fe. XRD observations indicated a slight increase in d002/d003 peak ratio, which could possibly be accounted for by a small amount of substitution of Fe into the octahedral layers of the montmorillonite. If correct, then this alteration might represent the early stages of conversion of the dioctahedral montmorillonite to an iron-rich dioctahedral smectite such as nontronite. Alternatively, the same effect may have been produced as a result of the displacement of exchangeable interlayer cations by Fe and subsequent conversion to form additional Fe-rich octahedral layers. In either case, the XRD results are consistent with the petrographical

  11. Mineralogical investigations of the interaction between iron corrosion products and bentonite from the NF-PRO Experiments (Phase 2)

    Energy Technology Data Exchange (ETDEWEB)

    Milodowski, A.E.; Cave, M.R.; Kemp, S.J.; Taylor, B.H.; Green, K.A.; Williams, C.L.; Shaw, R.A.; Gowing, C.J.B.; Eatherington, N.D. (British Geological Survey (United Kingdom))

    2009-01-15

    This report describes the findings of a second programme of work (Phase 2) undertaken by the British Geological Survey (BGS) on behalf of SKB, to characterise the mineralogical alteration of samples of compacted bentonite from experiments that SKB have co-funded in a study by Serco Assurance (Culham Laboratory, UK) to investigate the interaction of iron and bentonite, within the EU Framework 6 NF-PRO Project. Reacted bentonite residues from four NF-PRO Experiments - NFC1, NFC4, NFC7 and NFC13 were examined by BGS using; X-ray diffraction analysis (XRD); petrographical analysis with backscattered scanning electron microscopy (BSEM) with energy-dispersive X-ray microanalysis (EDXA) techniques, cation exchange capacity (CEC) and exchangeable cation analysis; and sequential chemical extraction. In addition, background chemical analysis of altered and background bentonite were also obtained by X-ray fluorescence spectrometry (XRFS). Bentonite immediately adjacent to corroding steel wires was found to have interacted with Fe released from the corroding metal. This resulted in the formation of narrow haloes of altered bentonite around the corroding steel wires, in which the clay matrix was significantly enriched in Fe. Similar observations were observed in bentonite around corroded iron coupons (observed in experiments NFC4 and NFC7 only), although the alteration zones were not as well developed in comparison to those around corroded steel wires. Detailed petrographical observation found no evidence for the formation discrete iron oxide or iron oxyhydroxide phases within the clay matrix but appeared to show that the clay particles themselves had become enriched in Fe. However, data from sequential chemical extraction suggests that a significant proportion (26 to 68%) of the iron in the altered bentonite is present as amorphous iron oxide or crystalline iron oxides (15 to 33% of the total iron). Some of the crystalline iron is present as primary magnetite and ilmenite

  12. Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu-Heng [Department; Pegis, Michael L. [Department; Mayer, James M. [Department; Stahl, Shannon S. [Department

    2017-11-07

    A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2 was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.

  13. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  14. Process and catalysts for the gasification of methanol. [German Patent

    Energy Technology Data Exchange (ETDEWEB)

    Harris, N.; Dennis, A.J.; Shevels, T.F.

    1975-02-13

    The invention concerns catalysts and catalytic processes for the gasification of methanol which is used to manufacture methane from methanol. Mixtures of iron and chromium oxide, phosphate, phosphoric acid, tungstate, tungstic acid, aluminium phosphate, aluminium oxide are suitable as dehydrating catalysts. Gasification takes place together with steam and dehydrogenating catalysts at high temperature. The molar ratios steam: methanol are described.

  15. Antipollution processing of a used refining catalyst and metal recovery

    Energy Technology Data Exchange (ETDEWEB)

    Trinh Dinh Chan; Llido, E.

    1992-04-30

    The used catalyst, containing metals such as vanadium, nickel and iron, is unloaded from the plant and is first processed by stripping; it is then calcined in critical conditions, and the catalyst metals are leached with a sodium hydroxide or sodium carbonate aqueous solution. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

  16. [Adsorption and removal of gas-phase Hg(0) over a V2O5/AC catalyst in the presence of SO2].

    Science.gov (United States)

    Wang, Jun-wei; Yang, Jian-li; Liu, Zhen-yu

    2009-12-01

    The adsorption and removal behaviors of gas-phase Hg(0) over V2O5/AC and AC were studied under a simulated flue gas (containing N2, SO2, O2) in a fixed-bed reactor. The influences of the V2O5, loading, SO2 concentration and adsorption temperature on Hg0 adsorption were investigated. The speciation of mercury adsorbed was determined by X-ray photoelectron spectroscopy (XPS). It was found that the V2O5/AC catalyst has a much higher capability than AC for Hg(0) adsorption and removal, mainly because of the catalytic oxidation activity of V2O5. The Hg(0) adsorption capability depends on the V2O5 content of the V2O5/AC catalyst. The amounts of mercury adsorbed increase from 75.9 microg x g(-1) to 89.6 microg x g(-1) (in the absence of O2) and from 115.9 microg x g(-1) to 185.5 microg x g(-1) (in the presence of O2) as the V2O5 loading increases from 0.5% to 1.0%, which are much higher than those over AC under the same conditions (9.6 microg x g(-1) and 23.3 microg x g(-1)). SO2 in the flue gas enhances Hg(0) adsorption over the V2O5/AC catalyst, which is due to the reaction of SO2 and Hg(0) on V2O3/AC. But as the SO2 concentration increases from 500 x 10(-6) to 2000 x 10(-6), the amount of mercury adsorbed has only a slight increase. The optimal temperature for Hg(0) adsorption over the V2O5/AC catalyst is around 150 degrees C, at which the amounts of mercury adsorbed are up to 98.5 microg x g(-1) (in the absence of O2) and 187.7 microg x g(-1) (in the presence of O2). The XPS results indicate the formation of Hg(0) and HgSO4 on the surface of the V2O5/AC catalyst, which confirms the role of V2O5 and SO2.

  17. Electrochemically induced C-H functionalization using bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl dual redox catalysts in a two-phase electrolytic system

    International Nuclear Information System (INIS)

    Li, Chao; Zeng, Cheng-Chu; Hu, Li-Ming; Yang, Feng-Lin; Yoo, Seung Joon; Little, R. Daniel

    2013-01-01

    Highlights: •Electrocatalytic C-H bond functionalization of tetrahydroisoquinolines is reported. •The transformation is mediated by a bromide ion/TEMPO dual redox catalyst system. •The transformation is conducted in a two-phase electrolytic medium. •The mechanism is proposed to proceed via a sequence of oxidation and addition reactions involving water as a nucleophile. •The procedure features wide substrate scope, the use of mild reaction conditions. -- Abstract: The electrochemical oxidative functionalization of benzylic C-H bonds, mediated by a dual bromide ion/2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) redox catalyst system in a two-phase electrolytic medium, has been explored using cyclic voltammetry (CV) and preparative electrolysis techniques. The results show that electron transfer between TEMPO + and a neutral substrate occurs with an efficiency that depends upon the presence of a base. The preparative scale electrolysis led to the formation of dihydro-isoquinolinones, isochromanone and xanthenone in moderate to excellent yields. On the basis of the CV analysis and preparative electrolysis results, a reaction mechanism is proposed

  18. Solution phase and membrane immobilized iron-based free radical reactions: Fundamentals and applications for water treatment

    Science.gov (United States)

    Lewis, Scott Romak

    Membrane-based separation processes have been used extensively for drinking water purification, wastewater treatment, and numerous other applications. Reactive membranes synthesized through functionalization of the membrane pores offer enhanced reactivity due to increased surface area at the polymer-solution interface and low diffusion limitations. Oxidative techniques utilizing free radicals have proven effective for both the destruction of toxic organics and non-environmental applications. Most previous work focuses on reactions in the homogeneous phase; however, the immobilization of reactants in membrane pores offers several advantages. The use of polyanions immobilized in a membrane or chelates in solution prevents ferric hydroxide precipitation at near-neutral pH, a common limitation of iron(Fe(II/III))-catalyzed hydrogen peroxide (H 2O2) decomposition. The objectives of this research are to develop a membrane-based platform for the generation of free radicals, degrade toxic organic compounds using this and similar solution-based reactions, degrade toxic organic compounds in droplet form, quantify hydroxyl radical production in these reactions, and develop kinetic models for both processes. In this study, a functionalized membrane containing poly(acrylic acid) (PAA) was used to immobilize iron ions and conduct free radical reactions by permeating H2O2 through the membrane. The membrane's responsive behavior to pH and divalent cations was investigated and modeled. The conversion of Fe(II) to Fe(III) in the membrane and its effect on the decomposition of hydrogen peroxide were monitored and used to develop kinetic models for predicting H2O2 decomposition in these systems. The rate of hydroxyl radical production, and hence contaminant degradation can be varied by changing the residence time, H2O2 concentration, and/or iron loading. Using these membrane-immobilized systems, successful removal of toxic organic compounds, such as pentachlorophenol (PCP), from water

  19. Non-Heme Iron Catalysts with a Rigid Bis-Isoindoline Backbone and Their Use in Selective Aliphatic C−H Oxidation

    NARCIS (Netherlands)

    Chen, Jianming; Lutz, Martin; Milan, Michela; Costas, Miquel; Otte, Matthias; Klein Gebbink, Bert

    2017-01-01

    Iron complexes derived from a bis-isoindoline-bis-pyridine ligand platform based on the BPBP ligand (BPBP=N,N′-bis(2-picolyl)-2,2′-bis-pyrrolidine) have been synthesized and applied in selective aliphatic C−H oxidation with hydrogen peroxide under mild conditions. The introduction of benzene

  20. Fe-BEA Zeolite Catalysts for NH3-SCR of NOx

    DEFF Research Database (Denmark)

    Frey, Anne Mette; Mert, Selcuk; Due-Hansen, Johannes

    2009-01-01

    Iron-containing zeolites are known to be promising catalysts for the NH3-SCR reaction. Here, we will investigate the catalytic activity of iron-based BEA catalysts, which was found to exhibit improved activities compared to previously described iron-containing zeolite catalysts, such as ZSM-5...... and ZSM-12. Series of Fe-BEA zeolite catalysts were prepared using a range of different preparation methods. Furthermore, we found that an iron concentration around 3 wt% on BEA showed a small optimum in SCR activity compared to the other iron loadings studied....

  1. Reduced cobalt phases of ZrO2 and Ru/ZrO2 promoted cobalt catalysts and product distributions from Fischer–Tropsch synthesis

    International Nuclear Information System (INIS)

    Kangvansura, Praewpilin; Schulz, Hans; Suramitr, Anwaraporn; Poo-arporn, Yingyot; Viravathana, Pinsuda; Worayingyong, Attera

    2014-01-01

    Highlights: • Ru/ZrO 2 , ZrO 2 promoted Co/SiO 2 for FTS were reduced by time resolved XANES. • Reduced catalysts resulted from XANES reduction showed the mixed phases of Co, CoO. • The highest percentages of CoO resulted from the high ZrO 2 promoted Co/SiO 2 . • Product distributions of 1-alkenes, iso-alkanes indicated sites for FTS and the 2° reaction. • Alkene readsorption were high corresponding to the high CoO forming branched alkanes. - Abstract: Co/SiO 2 catalysts were promoted with 4% and 8% ZrO 2 . Small amounts (0.07%) of Ru were impregnated onto 4%ZrO 2 /Co/SiO 2 . Catalysts resulting from time-resolved XANES reduction showed mixed phases of Co and CoO, with the highest percentages of Co resulting from Ru/4%ZrO 2 /Co/SiO 2 and the highest percentages of CoO resulting from 8%ZrO 2 /Co/SiO 2 . Product distributions of n-alkanes, iso-alkanes and alkenes during Fischer–Tropsch Synthesis (FTS) were used to investigate the catalyst performance of 4%ZrO 2 /Co/SiO 2 8%ZrO 2 /Co/SiO 2 and Ru/4%ZrO 2 /Co/SiO 2 . FTS steady state was studied by growth probabilities of n-alkane products. No 1-alkene was produced from Ru/4%ZrO 2 /Co/SiO 2 , indicating high availability of Fischer–Tropsch sites for long chain hydrocarbon growth, despite high methanation. Branched alkanes produced from the secondary reaction were related to the high CoO percentages on 8%ZrO 2 /Co/SiO 2 . Alkene readsorption sites were high, corresponding to the high CoO percentages, causing a high probability of forming branched alkane products

  2. O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Huasheng; Yin, Hengbo; Wang, Aili; Shen, Jun; Yan, Xiaobo; Liu, Yumin; Zhang, Changhua [Jiangsu University, Zhenjiang (China)

    2014-01-15

    Diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate was efficiently synthesized via the O-alkylation of disodium salt of diethyl 3,4-dihydroxy thiophene-2,5-dicarboxylate with 1,2-dichloroethane over ionic type phase transfer catalysts, such as tetrabutyl ammonium bromide and benzyl triethyl ammonium chloride. The ionic type phase transfer catalysts showed higher catalytic activities than the nonionic type phase transfer catalysts, such as triethylamine, pyridine, 18-crown-6, and polyethylene glycol 400/600, in the O-alkylation reaction. The conversion of the disodium salt of more than 97% and the selectivity of diethyl 3,4-ethylenedioxy thiophene-2,5-dicarboxylate of more than 98% were achieved when the O-alkylation reaction was synergistically catalyzed by tetrabutyl ammonium bromide and potassium iodide.

  3. Effective Liquid-phase Nitration of Benzene Catalyzed by a Stable Solid Acid Catalyst: Silica Supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40}

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Shu-wen; Liu, Li-jun; Zhang, Qian; Wang, Liang-yin [Liaocheng University, Liaocheng (China)

    2012-04-15

    Silica supported Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The Cs{sub 2.5}H{sub 0.5}PMo{sub 12}O{sub 40} particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology

  4. Separation and determination of polyurethane amine catalysts in polyether polyols by using UHPLC-Q-TOF-MS on a reversed-phase/cation-exchange mixed-mode column.

    Science.gov (United States)

    Li, Jiaxiao; Zhu, Marcel

    2018-02-01

    A simple, selective, and accurate ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry method was established and validated for the efficient separation and quantification of polyurethane amine catalysts in polyether polyols. Amine catalysts were primarily separated in polyether polyol-based sample by solid-phase extraction, and further baseline separated on a reversed-phase/cation-exchange mixed-mode column (SiELC Primesep™ 200) using 0.1% trifluoroacetic acid/acetonitrile as a mobile phase in gradient elution mode at a flow rate of 0.2 mL/min. High-resolution quadrupole time-of-flight mass spectrometry analysis in electrospray ionization positive mode allowed the identification as N,N'-bis[3-(dimethylamino)propyl]urea, N-[2-(2-dimethylaminoethoxy)ethyl]-N-methyl-1,3-propanediamine, and N,N,N',N'-tetramethyldipropylenetriamine. The method was validated and presented good linearity for all the analytes in blank matrices within the concentration range of 0.20-5.0 or 0.1-2.0 μg/mL with the correlation coefficients (R 2 ) ranging from 0.986 to 0.997. Method recovery ranged within 81-105% at all three levels (80, 100, and 120% of the original amount) with relative standard deviations of 1.0-6.2%. The limits of detection were in the range of 0.007-0.051 μg/mL. Good precision was obtained with relative standard deviation below 3.2 and 0.72% for peak area and retention time of three amines, respectively. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Efficient epoxidation of propene using molecular catalysts

    DEFF Research Database (Denmark)

    Markovits, Iulius I. E.; Anthofer, Michael H.; Kolding, Helene

    2014-01-01

    The epoxidation of propene is performed in homogeneous phase using various molecular catalysts and H2O2 or tert-butyl hydroperoxide as oxidants. A comparison between some molybdenum catalysts and methyltrioxorhenium (MTO) shows that the well known Re catalyst is the best among the examined...

  6. Morphology and phase structures of CW laser-induced oxide layers on iron surface with evolving reflectivity and colors

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Taotao, E-mail: wutaotao@nint.ac.cn; Wang, Lijun; Wei, Chenghua; Zhou, Menglian; He, Minbo; Wu, Lixiong

    2016-11-30

    Highlights: • Firstly, iron samples with different color features were obtained by continuous wave laser irradiation depending on progressive durations. The real-time reflectivity and temperature of samples were measured. The color and the reflectivity evolution were related. They were both caused by the forming oxide films. • Secondly, laser-induced oxidation process of iron was studied by microscope, X-ray diffraction and Raman spectrum. The first formed magnetite made the surface reflectivity decline rapidly and caused the “positive feedback” effect because of molecular absorption. The later formed hematite oscillated the reflectivity by interference effect. • Lastly, the laser-induced oxide films were thin, orientated and badly crystallized. The Wagner oxidation theory was incapable of describing the non-isothermal and early stage oxidation process. So we emphasized that a precise oxidation model depending on the experiment and the optical constants of the laser-induced oxides must be studied. - Abstract: Laser-induced oxidation will change the laser reflectivity and color features of metal surface. Both changes can be theoretically calculated based on the oxidation kinetics and the optical constants of oxides. For the purpose of calculation, the laser-induced oxidation process of pure polycrystalline iron was studied. Samples with various color features were obtained by continuous wave Nd:YAG fiber laser (1.06 μm) irradiation depending on progressive durations in the intensity of 1.90 W/cm{sup 2}. The real-time reflectivity and temperature were measured with integral sphere and thermocouples. The irradiated surface morphology and phase structures were characterized by microscope, X-ray diffraction and Raman spectrum. It was found that the first formed magnetite made the surface reflectivity decline rapidly and caused the “positive feedback” effect because of molecular absorption. The later formed hematite oscillated the reflectivity by

  7. Communicating catalysts

    Science.gov (United States)

    Weckhuysen, Bert M.

    2018-06-01

    The beauty and activity of enzymes inspire chemists to tailor new and better non-biological catalysts. Now, a study reveals that the active sites within heterogeneous catalysts actively cooperate in a fashion phenomenologically similar to, but mechanistically distinct, from enzymes.

  8. Quantum oscillations in the parent magnetic phase of an iron arsenide high temperature superconductor

    International Nuclear Information System (INIS)

    Sebastian, Suchitra E; Gillett, J; Lau, P H C; Lonzarich, G G; Harrison, N; Mielke, C H; Singh, D J

    2008-01-01

    We report measurements of quantum oscillations in SrFe 2 As 2 -which is an antiferromagnetic parent of the iron arsenide family of superconductors-known to become superconducting under doping and the application of pressure. The magnetic field and temperature dependences of the oscillations between 20 and 55 T in the liquid helium temperature range suggest that the electronic excitations are those of a Fermi liquid. We show that the observed Fermi surface comprising small pockets is consistent with the formation of a spin-density wave. Our measurements thus demonstrate that high T c superconductivity can occur on doping or pressurizing a conventional metallic spin-density wave state. (fast track communication)

  9. Formation of coatings from a liquid phase on the surface of iron-base alloys

    Directory of Open Access Journals (Sweden)

    A. Tatarek

    2008-12-01

    Full Text Available The study discloses the present state of the art regarding the technology and investigations of the phenomena that take place during the formation and growth of aluminum and zinc coatings hot-dip formed on iron products. In its cognitive aspect, the study offers an in-depth analysis of the partial processes that proceed in metal bath at the solid body – liquid metal interface. It is expected that the present study will help in a more detailed description of the respective phenomena and in full explanation of the mechanism of the coating growth, taking as an example the growth of aluminum coatings. The obtained results can serve as a background for some general conclusions regarding the thickness evolution process in other hot-dip coatings.

  10. New antipollution processing of a used refining catalyst and complete recovery of the catalyst metallic components

    Energy Technology Data Exchange (ETDEWEB)

    Trinh Dinh Chan; Llido, E.

    1992-05-15

    The used refining catalyst, containing metals such as vanadium, nickel and iron, is first processed by stripping; it is then calcined in critical conditions and heat processed in the presence of a melted alkaline base; the resulting solid matter is then water processed. The antipollution process can be applied to oil fraction hydroconversion or hydroprocessing catalysts.

  11. One-step liquid phase chemical method to prepare carbon-based amorphous molybdenum sulfides: As the effective hydrogen evolution reaction catalysts

    International Nuclear Information System (INIS)

    Guo, Mengmeng; Wu, Qikang; Yu, Miaomiao; Wang, Yinling; Li, Maoguo

    2017-01-01

    Two different kinds of carbon-based amorphous molybdenum sulfide composite catalysts (activated carbon supported amorphous molybdenum sulfide and acetylene black supported amorphous molybdenum sulfide) had been prepared in a facile and scalable one-step liquid phase chemical method. The morphological and structural information of catalysts was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and it’s electro-catalytic HER activity were evaluated by linear sweep voltammetry(LSV), amperometric i-t technology and AC impedance technology. The as-prepared carbon-based amorphous molybdenum sulfides showed greatly enhanced electro-catalytic activity for HER compared with pure amorphous molybdenum sulfides. Especially, the nano-sized acetylene black supported molybdenum sulfide exhibited excellent electro-catalytic HER performances with a low onset potential of −116 mV versus reverse hydrogen electrode (RHE) and a small Tafel slope of 51 mV per decade.

  12. Metamorphosis of the mixed phase PtRu anode catalyst for direct methanol fuel cells after exposure of methanol: In situ and ex situ characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Debasish [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Chorkendorff, Ib [Center for Individual Nanoparticle Functionality (CINF), Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Department of Physics, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark); Johannessen, Tue [Aerosol Laboratory, Nano.DTU, Department of Chemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby (Denmark)

    2007-11-08

    The change in the mixed phase heavily oxidized PtRu anode with the exposure of methanol in a direct methanol fuel cell (DMFC) has been investigated by electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD). The investigation had two major objectives: (i) to explore the original state of the active catalyst and (ii) to understand if alloying of Pt and Ru is a requirement for higher methanol oxidation activity. It was found that the methanol oxidation activity gradually improved for {proportional_to}2 h of exposure. The impedance spectra were taken at different times within this time of improvement of activity. The impedance spectra were deconvoluted in different contributions like membrane resistance (R{sub m}), charge transfer resistance (R{sub Ct}), adsorption resistance (R{sub ad}), and oxidation resistance (R{sub ox}). The improvement of the activity was explained in terms of the effect of the pretreatment on different contributions. XRD was done on the virgin and methanol exposed sample as a possible mean to identify the difference. It was postulated that the reduction of the as prepared PtRu after exposure was responsible for the activity improvement. Also, it was shown that bulk alloy formation is not a necessary condition for higher methanol activity of PtRu catalysts. (author)

  13. Phase mapping of iron-based rapidly quenched alloys using precession electron diffraction

    International Nuclear Information System (INIS)

    Svec, P.; Janotova, I.; Hosko, J.; Matko, I.; Janickovic, D.; Svec, P. Sr.; Kepaptsoglou, D. M.

    2013-01-01

    The present contribution is focused on application of PED and phase/orientation mapping of nanocrystals of bcc-Fe formed during the first crystallization stage of amorphous Fe-Co-Si-B ribbon. Using precession electron diffraction and phase/orientation mapping the formation of primary crystalline phase, bcc-Fe, from amorphous Fe-Co-Si-B has been analyzed. Important information about mutual orientation of the phase in individual submicron grains as well as against the sample surface has been obtained. This information contributes to the understanding of micromechanisms controlling crystallization from amorphous rapidly quenched structure and of the structure of the original amorphous state. The presented technique due to its high spatial resolution, speed and information content provided complements well classical techniques, especially in nanocrystalline materials. (authors)

  14. Aromatic chemicals by iron-catalyzed hydrotreatment of lignin pyrolysis vapor.

    Science.gov (United States)

    Olcese, Roberto Nicolas; Lardier, George; Bettahar, Mohammed; Ghanbaja, Jaafar; Fontana, Sébastien; Carré, Vincent; Aubriet, Frédéric; Petitjean, Dominique; Dufour, Anthony

    2013-08-01

    Lignin is a potential renewable material for the production of bio-sourced aromatic chemicals. We present the first hydrotreatment of lignin pyrolysis vapors, before any condensation, using inexpensive and sustainable iron-silica (Fe/SiO2 ) and iron-activated carbon (Fe/AC) catalysts. Lignin pyrolysis was conducted in a tubular reactor and vapors were injected in a fixed bed of catalysts (673 K, 1 bar) with stacks to investigate the profile of coke deposit. More than 170 GC-analyzable compounds were identified by GCxGC (heart cutting)/flame ionization detector mass spectrometry. Lignin oligomers were analyzed by very high resolution mass spectrometry, called the "petroleomic" method. They are trapped by the catalytic fixed bed and, in particular, by the AC. The catalysts showed a good selectivity for the hydrodeoxygenation of real lignin vapors to benzene, toluene, xylenes, phenol, cresols, and alkyl phenols. The spent catalysts were characterized by temperature-programmed oxidation, transmission electron microscopy (TEM), and N2 sorption. Micropores in the Fe/AC catalyst are completely plugged by coke deposits, whereas the mesoporous structure of Fe/SiO2 is unaffected. TEM images reveal two different types of coke deposit: 1) catalytic coke deposited in the vicinity of iron particles and 2) thermal coke (carbonaceous particles ≈1 μm in diameter) formed from the gas-phase growth of lignin oligomers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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...

  16. Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

    Science.gov (United States)

    Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

  17. Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

    Directory of Open Access Journals (Sweden)

    Jia Luo

    2011-01-01

    Full Text Available Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno}pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.

  18. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Directory of Open Access Journals (Sweden)

    Alexandre Luiz de Souza Pereira

    2011-01-01

    Full Text Available This work describes a three-step pre-treatment route for processing spent commercial NiMo/Al2O3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L-1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate.

  19. The importance of pre-treatment of spent hydrotreating catalysts on metals recovery

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Alexandre Luiz de Souza; Silva, Cristiano Nunes da; Afonso, Julio Carlos, E-mail: julio@iq.ufrj.b [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica; Mantovano, Jose Luiz [Instituto de Engenharia Nuclear (CNEN/IEN-RJ), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares

    2011-07-01

    This work describes a three-step pre-treatment route for processing spent commercial Ni Mo/Al{sub 2}O{sub 3} catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L{sup -1} sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate. (author)

  20. Efficient Air Desulfurization Catalysts Derived from Pig Manure Liquefaction Char

    Directory of Open Access Journals (Sweden)

    Rajiv Wallace

    2017-11-01

    Full Text Available Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2 was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H2S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H2S removal can be obtained from pig manure liquefaction wastes.

  1. {gamma} alumina- and HY zeolite-supported molybdenum catalysts: characterisation of the oxidic and sulfided phases; Catalyseurs a base de molybdene supporte sur alumine {gamma} et zeolithe HY: caracterisation des phases oxydes et sulfures

    Energy Technology Data Exchange (ETDEWEB)

    Plazenet, G

    2001-10-01

    Oxidic precursors of hydro-treatment catalysts (Co)Mo/alumina or zeolite were characterised by Raman spectroscopy, NMR and EXAFS at the Mo and Co K-edges. The formation of an Anderson-type alumino-molybdate compound upon impregnation of the support with an ammonium hepta-molybdate solution was confirmed for alumina, and also observed for the HY zeolitic support, with consumption of the amorphous alumina of the zeolite. In absence of the latter, ammonium hepta-molybdate precipitates. The species are conserved upon drying; upon calcination, the alumino-molybdate evolves into a surface aluminium molybdate type phase, whereas the hepta-molybdate transforms into MoO{sub 3}. The species formed upon impregnation are located in the inter-granular porosity whereas MoO{sub 3} vapor-condensation leads to formation of dimers located inside the zeolitic structure. The study of the cobalt-promoted precursors showed that the evolution of the molybdenum is the same in the case of co-impregnation preparation. Impregnation with cobalt-molybdate prevents the formation of the alumino-molybdate anion and thus enables the preservation of the Mo-Co interaction but, whatever the precursor, the leveling effect of the calcination-re-hydration steps was demonstrated. An EXAFS study at different sulfur coverages of the MoS{sub 2} platelets in the alumina-supported sulfided catalysts showed the limitations of EXAFS for size determination of MoS{sub 2} crystallites, a parameter that can be reached by AWAXS, which also conveys information about sheet-stacking. The EXAFS study of sulfided (Co)Mo/HY systems revealed incomplete sulfidation of the samples and the very high dispersion of the active phase. The absence of an observable Mo-Co interaction whatever the preparation of the promoted catalysts is consistent with the absence of promoting effect in toluene hydrogenation. (author)

  2. Morphology and Phase Composition of Particles Produced by Electro-Discharge-Machining of Iron

    International Nuclear Information System (INIS)

    Cabanillas, E. D.; Pasqualini, E. E.; Lopez, M.; Cirilo, D.; Desimoni, J.; Mercader, R. C.

    2001-01-01

    Towards producing metallic particles of controlled size and spherical shape, which are of technological importance, we have collected in the filters of an electro-discharge-machine (EDM) the material ejected from the surface of EDM iron pieces. The conditions of machining were varied for kerosene and water as dielectrics, using a discharge current of 25 A and duration times of 16 and 3072 μs for kerosene and of 32, 384 and 768 μs for water, respectively. Scanning electron microscopy was used to assess the effect of the time of discharge on the size of the particles. Moessbauer spectroscopy and X-ray diffraction revealed that for kerosene EDM particles only cementite-like carbides of diverse stoichiometry were formed. While no oxide was found for kerosene spheres, the analyses showed that besides the main fraction of α-Fe, a small percentage of wuestite (and traces of hematite for the 384 μs sample) formed on the water EDM ones

  3. Morphology and Phase Composition of Particles Produced by Electro-Discharge-Machining of Iron

    Energy Technology Data Exchange (ETDEWEB)

    Cabanillas, E. D.; Pasqualini, E. E.; Lopez, M.; Cirilo, D. [Comision Nacional de Energia Atomica, Centro Atomico Constituyentes (Argentina); Desimoni, J.; Mercader, R. C. [Universidad Nacional de La Plata, Departamento de Fisica, IFLP, Facultad de Ciencias Exactas (Argentina)

    2001-05-15

    Towards producing metallic particles of controlled size and spherical shape, which are of technological importance, we have collected in the filters of an electro-discharge-machine (EDM) the material ejected from the surface of EDM iron pieces. The conditions of machining were varied for kerosene and water as dielectrics, using a discharge current of 25 A and duration times of 16 and 3072 {mu}s for kerosene and of 32, 384 and 768 {mu}s for water, respectively. Scanning electron microscopy was used to assess the effect of the time of discharge on the size of the particles. Moessbauer spectroscopy and X-ray diffraction revealed that for kerosene EDM particles only cementite-like carbides of diverse stoichiometry were formed. While no oxide was found for kerosene spheres, the analyses showed that besides the main fraction of {alpha}-Fe, a small percentage of wuestite (and traces of hematite for the 384 {mu}s sample) formed on the water EDM ones.

  4. A study on the isotopic exchange between hydrogen and water on a catalyst in the liquid phase; Etude de l'echange isotopique entre l'hydrogene et l'eau sur catalyseur en phase liquide

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Montarnal, R; Balaceanu, J C [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

    1958-07-01

    It is well known that catalytic exchange in the liquid phase offers many advantages over exchange in the gaseous phase; however the rate of reaction is much smaller in the former case. The object of the following work is to study the influence of the various parameters on which the reaction rate depends (pressure, temperature, concentration, agitation), to classify catalysts according to their activity and to determine the economic possibility of liquid phase exchange. (author) [French] Il est un fait bien connu que l'echange catalytique en phase liquide presente divers avantages, compare a l'echange en phase gazeuse; la vitesse de reaction est toute fois beaucoup plus faible que dans le premier cas. L'objet du present rapport est d'etudier l'influence des differents parametres agissant sur la vitesse de reaction (pression, temperature, concentration, agitation), de classer les catalyseurs en fonction de leur activite et d'evaluer les possibilites economiques de l'echange en phase liquide. (auteur)

  5. Reuse of Hydrotreating Spent Catalyst

    International Nuclear Information System (INIS)

    Habib, A.M.; Menoufy, M.F.; Amhed, S.H.

    2004-01-01

    All hydro treating catalysts used in petroleum refining processes gradually lose activity through coking, poisoning by metal, sulfur or halides or lose surface area from sintering at high process temperatures. Waste hydrotreating catalyst, which have been used in re-refining of waste lube oil at Alexandria Petroleum Company (after 5 years lifetime) compared with the same fresh catalyst were used in the present work. Studies are conducted on partial extraction of the active metals of spent catalyst (Mo and Ni) using three leaching solvents,4% oxidized oxalic acid, 10% aqueous sodium hydroxide and 10% citric acid. The leaching experiments are conducting on the de coked extrude [un crushed] spent catalyst samples. These steps are carried out in order to rejuvenate the spent catalyst to be reused in other reactions. The results indicated that 4% oxidized oxalic acid leaching solution gave total metal removal 45.6 for de coked catalyst samples while NaOH gave 35% and citric acid gave 31.9 % The oxidized leaching agent was the most efficient leaching solvent to facilitate the metal removal, and the rejuvenated catalyst was characterized by the unchanged crystalline phase The rejuvenated catalyst was applied for hydrodesulfurization (HDS) of vacuum gas oil as a feedstock, under different hydrogen pressure 20-80 bar in order to compare its HDS activity

  6. Toward stable nickel catalysts for aqueous phase reforming of biomass-derived feedstock under reducing and alkaline conditions

    NARCIS (Netherlands)

    Haasterecht, van T.; Ludding, C.C.I.; Jong, de K.P.; Bitter, J.H.

    2014-01-01

    Nickel nanoparticles supported on carbon nanofibers (CNF) can be stabilized in aqueous phase processes at elevated temperatures and pressures by tuning the reaction conditions to control Ni oxidation and leaching. As a showcase, Ni/CNF was used for the production of hydrogen via aqueous phase

  7. 40 CFR 90.427 - Catalyst thermal stress resistance evaluation.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Catalyst thermal stress resistance... Gaseous Exhaust Test Procedures § 90.427 Catalyst thermal stress resistance evaluation. (a) The purpose of... catalyst conversion efficiency for Phase 1 engines. The thermal stress is imposed on the test catalyst by...

  8. Distribution and Influence of Iron Phases on the Physico-Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVAT SAID HASSAN; SAYED MAHMOUD SALEM

    2002-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD, DTA, dissolution analysis (DCB), IR, Mossbauer and X-band Electron Spin Resonance (ESR) spectroscopies. The purity of the samples and the degree of structural order were determined by XRD. The location of Fe in the octahedral sheet is characterized by absorption bands at ~875 cm-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron. The Mossbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe3+, in addition to third doubler with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample. 6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples. Goethite was confirmed by both IR and DTA. Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles. This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure. However, extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand, amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection, color, brightness and vitrification range of these kaolinite samples.

  9. Distribution and Influence of Iron Phases the Physico—Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVATSAIDHASSAN; SAYEDMAHMOUDSALEM

    2001-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-ray Electron Spin Resonance(ESR) spectroscopes.The purity of the samples and the degree of their structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron.The Moessbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe3+,in addition to third doublet with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample.Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samplas by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection,color,brightness and vitrification range of these kaolinite samples.

  10. Distribution and Influence of Iron Phases on the Physico-Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVAT SAID HASSAN; SAYED MAHMOUD SALEM

    2001-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD, DTA, dissolution analysis (DCB), IR, Mossbauer and X-ray Electron Spin Resonance (ESR) spectroscopes. The purity of the samples and the degree of their structural order were determined by XRD. The location of Fe in the octahedral sheet is characterized by absorption bands at ~875cm-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron. The Mossbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe3 + , in addition to third doublet with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H) sample. Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples. Goethite was confirmed by both IR and DTA. Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles. This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure. However, extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand, the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection, color, brightness and vitrification range of these kaolinite samples.

  11. Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates

    Institute of Scientific and Technical Information of China (English)

    MERVATSAIDHASSAN; SAYEDMAHMOUDSALEM

    2002-01-01

    Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe3+,in addition to third doubler with hyperfine parameter typical of Fe2+ in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.

  12. Lunar CATALYST

    Data.gov (United States)

    National Aeronautics and Space Administration — Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) is a NASA initiative to encourage the development of U.S. private-sector robotic lunar...

  13. Iron loading effects in Fe/SSZ-13 NH3-SCR catalysts: nature of the Fe-ions and structure-function relationships

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Zheng, Yang; Kukkadapu, Ravi K.; Wang, Yilin; Walter, Eric D.; Schwenzer, Birgit; Szanyi, Janos; Peden, Charles HF

    2016-05-06

    Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, a series of Fe/SSZ-13 catalysts with various Fe loadings were synthesized. UV-Vis, EPR and Mössbauer spectroscopies, coupled with temperature programmed reduction and desorption techniques, were used to probe the nature of the Fe sites. The major monomeric and dimeric Fe species are extra-framework [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+. Larger oligomers with unknown nuclearity, poorly crystallized Fe2O3 particles, together with isolated Fe2+ ions, are minor Fe-containing moieties. Reaction rate and Fe loading correlations suggest that isolated Fe3+ ions are the active sites for standard SCR while the dimeric sites are the active centers for NO oxidation. NH3 oxidation, on the other hand, is catalyzed by sites with higher nuclearity. A low-temperature standard SCR reaction network is proposed that includes redox cycling of both monomeric and dimeric Fe species, for SCR and NO2 generation, respectively. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Program 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.

  14. Kinetics and Pathways for the Debromination of Polybrominated Diphenyl Ethers by Bimetallic and Nanoscale Zerovalent Iron: Effects of Particle Properties and Catalyst

    Science.gov (United States)

    Zhuang, Yuan; Jin, Luting; Luthy, Richard G.

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe° slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe° nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe° nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe° are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe° reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role. PMID:22732301

  15. Synthesis of iron-based metal-organic framework MIL-53 as an efficient catalyst to activate persulfate for the degradation of Orange G in aqueous solution.

    Science.gov (United States)

    Pu, Mengjie; Guan, Zeyu; Ma, Yongwen; Wan, Jinquan; Wang, Yan; Brusseau, Mark L; Chi, Haiyuan

    2018-01-05

    A series of MIL-53(Fe) materials were synthesized using a solvothermal method under different temperature and time conditions and were used as catalysts to activate persulfate and degrade Orange G (OG). Influences of the above conditions on the crystal structure and catalytic behavior were investigated. Degradation of OG under different conditions was evaluated, and the possible activation mechanism was speculated. The results indicate that high synthesis temperature (larger than 170 °C) leads to poor crystallinity and low catalytic activity, while MIL-53(Fe) cannot fully develop at low temperature (100 or 120 °C). The extension of synthesis time from 5 h to 3 d can increase the crystallinity of the samples, but weakened the catalytic activity, which was caused by the reduction of BET surface area and the amount of Fe (II)-coordinative unsaturated sites. Among all the samples, MIL-53(Fe)-A possesses the best crystal structure and catalytic activity. In optimal conditions, OG can be totally decolorized after degradation for 90 min, and a removal rate of 74% for COD was attained after 120 min. The initial solution pH had great influence on OG degradation, with the greatest removal in acidic pH environment. ESR spectra showed that sulfate radical (SO 4 - ·), hydroxyl radical (OH·), persulfate radical (S 2 O 8 - ·), and superoxide radical (O 2 ·) exist in this system under acidic conditions. Furthermore, with the increase of pH, the relative amount of O 2 · increases while that of OH· and SO 4 - · decreases, resulting in a reduced oxidizing capacity of the system.

  16. Alternative alkali resistant deNOx catalysts

    DEFF Research Database (Denmark)

    Putluru, Siva Sankar Reddy; Kristensen, Steffen Buus; Due-Hansen, Johannes

    2012-01-01

    by onepot sol–gel method. All catalysts were characterized by BET, XRPD and NH3-TPD. Initial SCR activities of 8 out of 9 catalysts showed higher NO conversion at least at one temperature in the temperature range 300–500 ◦C compared to the conventional V2O5-WO3/TiO2 catalyst. After potassium poisoning (100......Alternative alkali resistant deNOx catalysts were prepared using three different supports ZrO2, TiO2 and Mordenite zeolite. The majority of the catalysts were prepared by incipient wetness impregnation of a commercial support, with vanadium, copper or iron precursor, one catalyst was prepared......–130 µmol of K/g of catalyst) the relative drop in SCR activity and acidity was lower for all the alternative catalysts compared to the industrial V2O5-WO3/TiO2 catalyst. Furthermore, Cu/MOR and Nano-V2O5/Sul-TiO2 catalysts showed 8–16 times higher SCR activities than the conventional even after high...

  17. Atomic level study of water-gas shift catalysts via transmission electron microscopy and x-ray spectroscopy

    Science.gov (United States)

    Akatay, Mehmed Cem

    Water-gas shift (WGS), CO + H2O ⇆ CO2 + H2 (DeltaH° = -41 kJ mol -1), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2O3 catalysts are employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism. In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy and X-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors of the catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization of nanostructures. Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety of nanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo2C is explored by forming Mo 2C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.

  18. Heat Treatment of Iron-Carbon Alloys in a Magnetic Field (Phase 2)

    Energy Technology Data Exchange (ETDEWEB)

    Ludtka, Gerard Michael [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-11-01

    Thermomagnetic processing was shown to shift the phase transformation temperatures and therefore microstructural evolution in the high performance engine valve spring 9254 steel alloy by applying a high magnetic field during cooling. These effects would be anticipated to improve performance such as high cycle fatigue as demonstrated in prior projects. Thermomagnetic processing of gears and crank shafts was constrained by the size of the prototype equipment currently available at ORNL. However, the commercial procurement viability of production scale 9-Tesla, 16-inch diameter bore thermomagnetic processing equipment for truck idler gears up to ~11-inch diameter and potential crank shaft applications was shown, as multiple superconducting magnet manufacturing companies (in conjunction with an induction heat treating company, AjaxTOCCO Magnethermic) offered cryogen-free or cryocooler equipment designs to Cummins.

  19. Phase transformation and magnetic anisotropy of an iron-palladium ferromagnetic shape-memory alloy

    International Nuclear Information System (INIS)

    Cui, J.; Shield, T.W.; James, R.D.

    2004-01-01

    Martensitic phase transformations in an Fe 7 Pd 3 alloy were studied using various experimental techniques: visual observation, differential scanning calorimeter (DSC) measurements and X-ray diffraction. Magnetic measurements on this alloy were made using a vibrating sample magnetometer (VSM) and a Susceptibility Kappa bridge. The VSM measurements were made with the sample in a compression fixture to bias the martensite phase to a single variant. Both X-ray and DSC measurements show that the FCC-FCT transformation is a weak first-order thermoelastic transition. The average lattice parameters are a=3.822±0.001 A and c=3.630±0.001 A for the FCT martensite, and a 0 =3.756±0.001 A for the FCC austenite. The latent heat of the FCC-FCT transformation is 10.79±0.01 J/cm 3 . A Susceptibility Kappa bridge measurement determined the Curie temperature to be 450 deg. C. The saturation magnetization from VSM data is m s =1220±10 emu/cm 3 at -20 deg. C for the martensite and m s =1080±10 emu/cm 3 at 60 deg. C for the austenite. The easy axes of a single variant of FCT martensite are the [1 0 0] and [0 1 0] directions (the a-axes of the FCT lattice) and the [0 0 1] direction (FCT c-axis) is the hard direction. The cubic magnetic anisotropy constant K 1 is -5±2x10 3 erg/cm 3 for the austenite at 60 deg. C, and the tetragonal anisotropy constant K 1 +K 2 is 3.41 ± 0.02 x 10 5 erg/cm 3 for the martensite at a temperature of -20 deg. C and under 8 MPa of compressive stress in the [0 0 1] direction

  20. Low Concentration Fe-Doped Alumina Catalysts Using Sol-Gel and Impregnation Methods: The Synthesis, Characterization and Catalytic Performance during the Combustion of Trichloroethylene

    Directory of Open Access Journals (Sweden)

    Carolina Solis Maldonado

    2014-03-01

    Full Text Available The role of iron in two modes of integration into alumina catalysts was studied at 0.39 wt% Fe and tested in trichloroethylene combustion. One modified alumina was synthesized using the sol-gel method with Fe added in situ during hydrolysis; another modification was performed using calcined alumina, prepared using the sol-gel method and impregnated with Fe. Several characterization techniques were used to study the level of Fe modification in the γ-Al2O3 phase formed and to correlate the catalytic properties during trichloroethylene (TCE combustion. The introduction of Fe in situ during the sol-gel process influenced the crystallite size, and three iron species were generated, namely, magnetite, maghemite and hematite. The impregnated Fe-alumina formed hematite and maghemite, which were highly dispersed on the γ-Al2O3 surface. The X-ray photoelectron spectra (XPS, FT-IR and Mössbauer spectroscopy analyses revealed how Fe interacted with the γ-Al2O3 lattice in both catalysts. The impregnated Fe-catalyst showed the best catalytic performance compared to the catalyst that was Fe-doped in situ by the sol-gel method; both had better catalytic activity than pure alumina. This difference in activity was correlated with the accessibility of the reactants to the hematite iron species on the surface. The chlorine poisoning for all three catalysts was less than 1.8%.